CA1210191A - Process for preparing imidized acrylic polymers - Google Patents
Process for preparing imidized acrylic polymersInfo
- Publication number
- CA1210191A CA1210191A CA000405890A CA405890A CA1210191A CA 1210191 A CA1210191 A CA 1210191A CA 000405890 A CA000405890 A CA 000405890A CA 405890 A CA405890 A CA 405890A CA 1210191 A CA1210191 A CA 1210191A
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- CA
- Canada
- Prior art keywords
- polymer
- amine
- temperature
- ammonia
- extruder
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
An improved process for preparing imidized acrylic polymers, which process is carried out continuously by reacting an acrylic polymer with ammonia or an amine in an internally baffled tubular reaction vessel.
An improved process for preparing imidized acrylic polymers, which process is carried out continuously by reacting an acrylic polymer with ammonia or an amine in an internally baffled tubular reaction vessel.
Description
` ` ~2~
TITLE
Process for Preparin~
Imidized Acrylic Polymers FIELD OF THE INVENTION
This invention relates to a proce~s for imidizing acrylic polymers; and more particularly to a continuous process carried out in an in~ernally baffled tube.
BACR~ROUND OF TB~ INVENTION
Methyl methacrylate ~MA~ homopolymer and copolymers with, e.g., acrylates, styrene or butadiene, can be imidized by reacting the polymer with ammonia or alkyl- or aryl- amines to form imide~
as shown in th~ e~uation following:
C~3 CH3 CH3 D ~H~ ~CH3 ~--CH2~ 2~C ~ H~--C C--C-O ~=C R~
The cyclic imide polymers can also be obtained by heating selected amides or nitriles.
Most such processes are batch operations. Recently a continuous imidization procedure was described in U.S. Patent 4,246,374 in which a methacrylate or acrylate polymPr is placed in a vented screw extruder with an amine and the imide is formed as the materials are moved through the extruder at elevated temperatures under essentially anhydrous conditions.
SUMMARY OF THE INVENTION
A novel continuous process for imidizing methacrylic and acrylic resins has now been found which does not need to employ a screw extruder and in which temperature and pressure can be more carefully controlled than in a screw extruder.
~D~5085 35 ~X~
0~
The novel process is a process for imidizin~
a methacrylate or acrylate polymer which comprises in ~equence a) mixing a molten methacrylate or acrylate 5 polymer with ammonia or an alkyl- or aryl- primary amine 9 b~ introducing the molten mixture into a baffled tubular reactor which provides dispersed plug-~low, c) raising the temperature of the mixture inside ~he tubular reactor to between 200C and 300C, and d) conducting ~he molten mixture through the tubular reactor in a ~ime adequate to accomplish imidization but less than necessary for ~ubstantial degradation of polymer.
DESCRIPTION OF T~E INVENTIO~
The polymer to be imidized is an acrylic andjor methacrylic polymer. It conta~ns adjacent units of R
C~2 C~
C=O
R' wherein R is -CH3 or -~, and R' is alkyl of 1-10 carbon atoms. These polymers may also contain units derived from up to 40% by weight me~hacrylic or acrylic acid, styrene, butadiene, ethylene or acrylonitrile and the like. Polymers containing at least 75~ methyl ~ethacrylate are preferred. The molecular weight of the polymers may vary over a wide range. Those having an inherent viscosity of at least 0.3 measured in a .5% solution of mixture of methanol and methylene chloride (20~80) at 25C are preferred. The polymer to be imidized may be employed in any form, but generally the pol.ymer is in ~he form of powder or granules prior to melting.
The ammonia or alkyl- or aryl- primary amine employed generally will have the formula R"NH2 wherein R" is H, alkyl of 1-12 carbon atoms, cycloalkyl of 7 to 11 carbon atoms or aryl of 6-10 carbon atoms, preferably phenyl. Examples of amines 10 useful herein include methyl, ethyl, n-propyl, n-butyl, heptyl, hexyl, octyl, nonyl, decyl, dodecyl, hexadecyl, octadecyl, isobutyl, sec-butyl, t-butyl, isopropyl, 2-ethylhexyl, phenethyl, allyl, benzyl, para-chlorobenzyl and dimethoxyphenethyl amines;
1~ besides, alanine, glycine, 3'-aminoacetophenone,
TITLE
Process for Preparin~
Imidized Acrylic Polymers FIELD OF THE INVENTION
This invention relates to a proce~s for imidizing acrylic polymers; and more particularly to a continuous process carried out in an in~ernally baffled tube.
BACR~ROUND OF TB~ INVENTION
Methyl methacrylate ~MA~ homopolymer and copolymers with, e.g., acrylates, styrene or butadiene, can be imidized by reacting the polymer with ammonia or alkyl- or aryl- amines to form imide~
as shown in th~ e~uation following:
C~3 CH3 CH3 D ~H~ ~CH3 ~--CH2~ 2~C ~ H~--C C--C-O ~=C R~
The cyclic imide polymers can also be obtained by heating selected amides or nitriles.
Most such processes are batch operations. Recently a continuous imidization procedure was described in U.S. Patent 4,246,374 in which a methacrylate or acrylate polymPr is placed in a vented screw extruder with an amine and the imide is formed as the materials are moved through the extruder at elevated temperatures under essentially anhydrous conditions.
SUMMARY OF THE INVENTION
A novel continuous process for imidizing methacrylic and acrylic resins has now been found which does not need to employ a screw extruder and in which temperature and pressure can be more carefully controlled than in a screw extruder.
~D~5085 35 ~X~
0~
The novel process is a process for imidizin~
a methacrylate or acrylate polymer which comprises in ~equence a) mixing a molten methacrylate or acrylate 5 polymer with ammonia or an alkyl- or aryl- primary amine 9 b~ introducing the molten mixture into a baffled tubular reactor which provides dispersed plug-~low, c) raising the temperature of the mixture inside ~he tubular reactor to between 200C and 300C, and d) conducting ~he molten mixture through the tubular reactor in a ~ime adequate to accomplish imidization but less than necessary for ~ubstantial degradation of polymer.
DESCRIPTION OF T~E INVENTIO~
The polymer to be imidized is an acrylic andjor methacrylic polymer. It conta~ns adjacent units of R
C~2 C~
C=O
R' wherein R is -CH3 or -~, and R' is alkyl of 1-10 carbon atoms. These polymers may also contain units derived from up to 40% by weight me~hacrylic or acrylic acid, styrene, butadiene, ethylene or acrylonitrile and the like. Polymers containing at least 75~ methyl ~ethacrylate are preferred. The molecular weight of the polymers may vary over a wide range. Those having an inherent viscosity of at least 0.3 measured in a .5% solution of mixture of methanol and methylene chloride (20~80) at 25C are preferred. The polymer to be imidized may be employed in any form, but generally the pol.ymer is in ~he form of powder or granules prior to melting.
The ammonia or alkyl- or aryl- primary amine employed generally will have the formula R"NH2 wherein R" is H, alkyl of 1-12 carbon atoms, cycloalkyl of 7 to 11 carbon atoms or aryl of 6-10 carbon atoms, preferably phenyl. Examples of amines 10 useful herein include methyl, ethyl, n-propyl, n-butyl, heptyl, hexyl, octyl, nonyl, decyl, dodecyl, hexadecyl, octadecyl, isobutyl, sec-butyl, t-butyl, isopropyl, 2-ethylhexyl, phenethyl, allyl, benzyl, para-chlorobenzyl and dimethoxyphenethyl amines;
1~ besides, alanine, glycine, 3'-aminoacetophenone,
2-aminoanthraquinone and p-aminobenzoic acid. Other suitable amine~ are cyclohexylamine, 2-amino ~,6-dime~hylpyridine, ~-aminophthalimide, 2-aminopyrimidine, 2-aminothiazole, S-aminothiazole, 2~ 5-amino-1-H-tetrazole, aniline, bromoaniline, dibromoaniline, tribromoaniline, chloroaniline, dichloroaniline~ trichloroaniline, p-phenetidine and p-toluidine.
In ~he process of this invention the polymer in molten form and ammonia or amine are mixed just prior to or just after entry înto the tubular reactorO One method of mixing i5 to feed the polymer into an extruder to melt the polymer and to propel the molten polymer into the tubular reactor. Once the polymer is melted, the ammonia or amine can be added. Care is taken to add the ammonia or amine just prior to or just after entry into the tubular reactor. Addition earlier than that may lead to some premature reaction, thus rendering useless the ~2~
careful temperature and pressure control obtained by carrying out the reaction in the tubular reactor.
~ emperatures of reaction are as l~w as can be used to maintain ~ short reac~ion time and as high 5 as can be tolerated to avoid excessive degradation of the polymer. Use of an internally baffled tubular r~actor with high efficiency of mixing and the attendant uniformity of temperatures across contained materials permit the use of ~hort reac~ion times a~
relatively high temperatures withou~ a fear of hot spots in ~he reaction medium. Such hot spo~s and uneven radial temperature distribution result in degradation of the polymer and otherwise unacceptable or undesirable polymeric material. Wher~ residence time of cont3ined materials can be maintained practically constant and where temperature gradients perpendicular to the axis of flow can be maintained very low, it has been found advantageous ~o conduct the reaction at high temperatures with short time rather than at low temperatures with longer time.
Important factors for successfully accomplishing the reaction include close overall con~rol of the temperature of reactant materials and maintenance of a short and uniform residence time of materials in the reactor. If there are large temperature differences within the reactant melt, there will be inconsistent degrees of reaction, i.e., incomplete reaction in low temperature zones and polymer degradation in high temperature zones. In a tubular reactor, the temperature differences perpendicular to gross material flow ~radially) must be minimized. To minimize such temperature differences, there must be efficient radial dispersion of materials in order that heat transfer will occur from one location in ~he reactor, radially, to another. Axial temperature control is also important to prevent inconsistent degrees of reaction which might arise from varying exposure to proper temperatures of reaction~ A steady state 5 operation is necessary for conducting acceptable continuous reaction processes, A reactor which exhibits the required ~emperature control, ~ffi~iency in heat transfer, and uniformity of residence time, is a tubular reactor internally fitted with a series 10 of helix baffles of alternating opposite pitch. Such a reactor is disclosed in U.S. Patent No. 3,286,992.
To achieve a polymer of uniform guality, it is important that all of the reactant material be exposed to substantizlly the æame reaction 15 temperatures for ~ubstantially ~he same time. This is def ined as "dispersed plug flow". 5uch dispersed plug flow provide that each element of molten polymer is in the reactor for substantially the same time and that there is considerable movement of 20 domains of the molten polymer with respe~t ~o other domains of the molten polymer in a radial direction, rather than in an axial or longitudinal d;rection.
In the present process, the polymer is heated to the reaction temperature prior to entry into the reactor, and the ammonia or amine is added just prior to or just after entry. In the reactor, the temperature is maintained at ~00C to 300C, preferably 240 to 280~C. In the reactor the reactants are intimately mixed and each element of material experiences practically the same reaetion temperature for practically the same duration. The duration of reaction is generally less than about ten minutes and more than about one-quarter minute. The most preferred duration is fr~m about five minutes to about one-half minute - the shorter maximum time being important to prevent excessive degradation, crosslinking, and other undesirable side reactions.
It has been found that close temperature control, small radial temper~ture gradients, and 5 uniform, short residence time permit good reaction without excessive degradation which would be expected at the high temperature. On completion of the reaction, the resulting imide is removed and vola~iles vented. The resulting imide is then cooled 10 and cut into pellets.
The degree of imidization of the acryli~
polymer can easily be controlled in the process a~cording to the invention and various degrees of imidlzation can be reachcd as a function of the desired properties. The desired degree of imidization can be adjusted easily through adjustment o the reaction parameters, ~uch as the dwell time and the temperature. Although imidizatson of the polymer as low as only 1% is possible, as a rule, an imidization of at least 10% is effected, to reach a noteworthy improvement in properties of the acrylic polymer.
No catalyst is required in the process according to the invention. This has the great advantage that removal of the catalys~ is dispensed with. ~owever, small quantities of a catalyst can increase the reaction velocity if desired.
A solvent is not necesjary in the process of this invention and it is preferred to operate in the absence of a solvent. ~owever, if desired, a solvent may be used to decrease the viscosity of the molten mass or to carry a catalyst.
The imides made by the process of this invention are useful as thermoplastic moldin~ resins, and can be extruded in the form of fibers, tubes or ~2~
film and the like. The molding resins can be used to prepare molded articles such as toys, pens, housings, etc.
The process of this invention is 5 particularly useful in preparing imides which contain 1-40 weight percent cyclic anhydride units. These imides thus contain recurring units of a) R
. 'CH2-C - _ C=~
0~' ~ CH2 c ~ ~ C ~
Lo~c~o c~o~
2d c ~ ~ CH2`~ R
_ - C~2-C ~--_ 0 ~7 0 R"
wherein R is -C~3 or -H: R' is alkyl of 1-10 carbon atoms; and R" is H, alkyl of 1-10 carb~ns, cycloalkyl of 7-11 carbons, cyclophenyl, or phenylalkyl of 7-9 carbon atoms wherein the phenyl groups can contain lower alkyl, lower alkoxy or halo su~stituents; and wherein units of a) con~titute 20 to 94 weight percent of the recurring units, units of b) constitute 1-40 weight percent of the recurring units, and units of c) constitute 5-8G weight percent of the recurring units, said percents totaling 100%.
DESCRIPTION OF PREFERRED EMBODIMENTS
In the following examples, polymer is hea-ted and fed to and through a baffled tubular reactor by means of force provided by a screw extruder. The internally-baffled tubular reactor exhibiting dispersed plug flow used in the examples was supplied by the Kenics Corporation, Danvers, Mass., U.S.A.
A one-inch Killian~ extruder with a vacuum port and two-stage screw was fitted at its die exit with an adaptor plate, three one-inch diameter Kenics Thermogenizer~ sections in succession Eollowed by a valve die. The Killian extruder was used to melt and move the polymer into the Kenics sections. A
diffusion plate 1/8" thick with 64 holes was placed in the leading Kenics edge. This plate, used to aid mixing, was about 1" downstream of an injection probe exiting 1/4" into the melt stream (fitted into an adaptor plate) and about 1 1/2" upstream of the first element of the first Kenics section. Ammonia or amine was entered through the injec-tion probe or through the vent port of the Killian extruder. A
screen pack was placed after the last Kenics section and before the valve die to aid in pressure control.
A heated transfer pipe was used to convey the melt from the valve die to the rear vacuum part of a Werner and Pfliederer* 28-mm twin screw extruder which was used to remove volatiles. The feed throat of the 28-mm extuder was used as a vacuum to vent volatiles and the front vacuum port was used to devolatilize the imide product as well. The emerging imide strand was then quenched and cut.
Unless otherwise indicated~ percentages are by weight.
* denotes trade mark ~.2~
Thi~ example demonstrates that the imidization reaction occurs in the baffled ~ubular reactor and no~ in either of ~he ex~ruders. Two fine (DY) and two coarse (CY) Koch~ baffled plug-flow mixers replaced the leading Kenics elements in the first of the three Kenics secticns and two coarse (CY) Koch~ elements replaced he leading Kenics elements in the second Renics section. The 1"
Killian extruder was run at 144 rpm wi~h temperature settings of 250~C rear zone, 225C center 20ne, and 225C ~ront zone. The Kenics sections were all set ~o provide a t~mperature of 280C; ~he die Yalve and the ~ransfer pipe were set at 225C. The 28-mm twin ~crew extruder had a straight through screw design with ~he exception of one set of reverse elements between the two regular vac~um ports to provide a melt ~eal. I~ was run between 108 and 135 rpm with the following temperature settings: rear ~1) a 50C~
~2) z 200DC, (3), (4), (5), and die - 250C.
Four batches were run using cyclohexyl amine and polyme~hyl me~hacryla~e of IV of between .47 and . 53 . Dur ing ba~ches 1 and 2 the ~mine was pumped into the vacuum port of the 1'l Rillian extruder 25 during ba~ches 3 and 4, i~ was pumped in~o the injection probe set into the adaptor plate. In ba~ches 1 and 3 the final product was isolated as cut pellets after it was devolatilized in the 28-mm extruder, ~or batches 2 and 4 samples were removed 30 from a melt thermocouple hole at the downstream end of the transfer pipe just prior to where the melt would come in contact with the screw of the twin screw e~truder. Table 1 shows that 63% of the amine reacted with polymer when mixed solely in the tubular 35 reactor ~batches 3 and 4) and that only 57% of ~he ~L2~L9~
amine reacted with polymer when amine was entered into the Rillian extruder and product was passed through the twin screw extruder (batch 1~. Since higher conversion was obtained in batches 3 and 4 than in batch 1, one can conclude ~hat the reaction occurs in the tubular reactor.
Finished ~ N
Amine Polymer in Amine Pump Pumped Product~ Final Con~
Pressure In At: ion Rate Pro- % ver-Batch (Psi) (ml/min) ~/minl du~t Imide sion . .
1 900 12.5 38.6 2.~4 37.5 57%
2 ~00 12.5 ~* 2.35 39.3 Not ~easured
In ~he process of this invention the polymer in molten form and ammonia or amine are mixed just prior to or just after entry înto the tubular reactorO One method of mixing i5 to feed the polymer into an extruder to melt the polymer and to propel the molten polymer into the tubular reactor. Once the polymer is melted, the ammonia or amine can be added. Care is taken to add the ammonia or amine just prior to or just after entry into the tubular reactor. Addition earlier than that may lead to some premature reaction, thus rendering useless the ~2~
careful temperature and pressure control obtained by carrying out the reaction in the tubular reactor.
~ emperatures of reaction are as l~w as can be used to maintain ~ short reac~ion time and as high 5 as can be tolerated to avoid excessive degradation of the polymer. Use of an internally baffled tubular r~actor with high efficiency of mixing and the attendant uniformity of temperatures across contained materials permit the use of ~hort reac~ion times a~
relatively high temperatures withou~ a fear of hot spots in ~he reaction medium. Such hot spo~s and uneven radial temperature distribution result in degradation of the polymer and otherwise unacceptable or undesirable polymeric material. Wher~ residence time of cont3ined materials can be maintained practically constant and where temperature gradients perpendicular to the axis of flow can be maintained very low, it has been found advantageous ~o conduct the reaction at high temperatures with short time rather than at low temperatures with longer time.
Important factors for successfully accomplishing the reaction include close overall con~rol of the temperature of reactant materials and maintenance of a short and uniform residence time of materials in the reactor. If there are large temperature differences within the reactant melt, there will be inconsistent degrees of reaction, i.e., incomplete reaction in low temperature zones and polymer degradation in high temperature zones. In a tubular reactor, the temperature differences perpendicular to gross material flow ~radially) must be minimized. To minimize such temperature differences, there must be efficient radial dispersion of materials in order that heat transfer will occur from one location in ~he reactor, radially, to another. Axial temperature control is also important to prevent inconsistent degrees of reaction which might arise from varying exposure to proper temperatures of reaction~ A steady state 5 operation is necessary for conducting acceptable continuous reaction processes, A reactor which exhibits the required ~emperature control, ~ffi~iency in heat transfer, and uniformity of residence time, is a tubular reactor internally fitted with a series 10 of helix baffles of alternating opposite pitch. Such a reactor is disclosed in U.S. Patent No. 3,286,992.
To achieve a polymer of uniform guality, it is important that all of the reactant material be exposed to substantizlly the æame reaction 15 temperatures for ~ubstantially ~he same time. This is def ined as "dispersed plug flow". 5uch dispersed plug flow provide that each element of molten polymer is in the reactor for substantially the same time and that there is considerable movement of 20 domains of the molten polymer with respe~t ~o other domains of the molten polymer in a radial direction, rather than in an axial or longitudinal d;rection.
In the present process, the polymer is heated to the reaction temperature prior to entry into the reactor, and the ammonia or amine is added just prior to or just after entry. In the reactor, the temperature is maintained at ~00C to 300C, preferably 240 to 280~C. In the reactor the reactants are intimately mixed and each element of material experiences practically the same reaetion temperature for practically the same duration. The duration of reaction is generally less than about ten minutes and more than about one-quarter minute. The most preferred duration is fr~m about five minutes to about one-half minute - the shorter maximum time being important to prevent excessive degradation, crosslinking, and other undesirable side reactions.
It has been found that close temperature control, small radial temper~ture gradients, and 5 uniform, short residence time permit good reaction without excessive degradation which would be expected at the high temperature. On completion of the reaction, the resulting imide is removed and vola~iles vented. The resulting imide is then cooled 10 and cut into pellets.
The degree of imidization of the acryli~
polymer can easily be controlled in the process a~cording to the invention and various degrees of imidlzation can be reachcd as a function of the desired properties. The desired degree of imidization can be adjusted easily through adjustment o the reaction parameters, ~uch as the dwell time and the temperature. Although imidizatson of the polymer as low as only 1% is possible, as a rule, an imidization of at least 10% is effected, to reach a noteworthy improvement in properties of the acrylic polymer.
No catalyst is required in the process according to the invention. This has the great advantage that removal of the catalys~ is dispensed with. ~owever, small quantities of a catalyst can increase the reaction velocity if desired.
A solvent is not necesjary in the process of this invention and it is preferred to operate in the absence of a solvent. ~owever, if desired, a solvent may be used to decrease the viscosity of the molten mass or to carry a catalyst.
The imides made by the process of this invention are useful as thermoplastic moldin~ resins, and can be extruded in the form of fibers, tubes or ~2~
film and the like. The molding resins can be used to prepare molded articles such as toys, pens, housings, etc.
The process of this invention is 5 particularly useful in preparing imides which contain 1-40 weight percent cyclic anhydride units. These imides thus contain recurring units of a) R
. 'CH2-C - _ C=~
0~' ~ CH2 c ~ ~ C ~
Lo~c~o c~o~
2d c ~ ~ CH2`~ R
_ - C~2-C ~--_ 0 ~7 0 R"
wherein R is -C~3 or -H: R' is alkyl of 1-10 carbon atoms; and R" is H, alkyl of 1-10 carb~ns, cycloalkyl of 7-11 carbons, cyclophenyl, or phenylalkyl of 7-9 carbon atoms wherein the phenyl groups can contain lower alkyl, lower alkoxy or halo su~stituents; and wherein units of a) con~titute 20 to 94 weight percent of the recurring units, units of b) constitute 1-40 weight percent of the recurring units, and units of c) constitute 5-8G weight percent of the recurring units, said percents totaling 100%.
DESCRIPTION OF PREFERRED EMBODIMENTS
In the following examples, polymer is hea-ted and fed to and through a baffled tubular reactor by means of force provided by a screw extruder. The internally-baffled tubular reactor exhibiting dispersed plug flow used in the examples was supplied by the Kenics Corporation, Danvers, Mass., U.S.A.
A one-inch Killian~ extruder with a vacuum port and two-stage screw was fitted at its die exit with an adaptor plate, three one-inch diameter Kenics Thermogenizer~ sections in succession Eollowed by a valve die. The Killian extruder was used to melt and move the polymer into the Kenics sections. A
diffusion plate 1/8" thick with 64 holes was placed in the leading Kenics edge. This plate, used to aid mixing, was about 1" downstream of an injection probe exiting 1/4" into the melt stream (fitted into an adaptor plate) and about 1 1/2" upstream of the first element of the first Kenics section. Ammonia or amine was entered through the injec-tion probe or through the vent port of the Killian extruder. A
screen pack was placed after the last Kenics section and before the valve die to aid in pressure control.
A heated transfer pipe was used to convey the melt from the valve die to the rear vacuum part of a Werner and Pfliederer* 28-mm twin screw extruder which was used to remove volatiles. The feed throat of the 28-mm extuder was used as a vacuum to vent volatiles and the front vacuum port was used to devolatilize the imide product as well. The emerging imide strand was then quenched and cut.
Unless otherwise indicated~ percentages are by weight.
* denotes trade mark ~.2~
Thi~ example demonstrates that the imidization reaction occurs in the baffled ~ubular reactor and no~ in either of ~he ex~ruders. Two fine (DY) and two coarse (CY) Koch~ baffled plug-flow mixers replaced the leading Kenics elements in the first of the three Kenics secticns and two coarse (CY) Koch~ elements replaced he leading Kenics elements in the second Renics section. The 1"
Killian extruder was run at 144 rpm wi~h temperature settings of 250~C rear zone, 225C center 20ne, and 225C ~ront zone. The Kenics sections were all set ~o provide a t~mperature of 280C; ~he die Yalve and the ~ransfer pipe were set at 225C. The 28-mm twin ~crew extruder had a straight through screw design with ~he exception of one set of reverse elements between the two regular vac~um ports to provide a melt ~eal. I~ was run between 108 and 135 rpm with the following temperature settings: rear ~1) a 50C~
~2) z 200DC, (3), (4), (5), and die - 250C.
Four batches were run using cyclohexyl amine and polyme~hyl me~hacryla~e of IV of between .47 and . 53 . Dur ing ba~ches 1 and 2 the ~mine was pumped into the vacuum port of the 1'l Rillian extruder 25 during ba~ches 3 and 4, i~ was pumped in~o the injection probe set into the adaptor plate. In ba~ches 1 and 3 the final product was isolated as cut pellets after it was devolatilized in the 28-mm extruder, ~or batches 2 and 4 samples were removed 30 from a melt thermocouple hole at the downstream end of the transfer pipe just prior to where the melt would come in contact with the screw of the twin screw e~truder. Table 1 shows that 63% of the amine reacted with polymer when mixed solely in the tubular 35 reactor ~batches 3 and 4) and that only 57% of ~he ~L2~L9~
amine reacted with polymer when amine was entered into the Rillian extruder and product was passed through the twin screw extruder (batch 1~. Since higher conversion was obtained in batches 3 and 4 than in batch 1, one can conclude ~hat the reaction occurs in the tubular reactor.
Finished ~ N
Amine Polymer in Amine Pump Pumped Product~ Final Con~
Pressure In At: ion Rate Pro- % ver-Batch (Psi) (ml/min) ~/minl du~t Imide sion . .
1 900 12.5 38.6 2.~4 37.5 57%
2 ~00 12.5 ~* 2.35 39.3 Not ~easured
3 900 12.0 41.4 2.22 37.3 63%
1~ ~ goo 12.0 "* 2.~2 37~3 63%
*Could not be actually measured but no con~rols were ~hanged during short term of ~hese s~ates; ~herefore, rates probably unchan~ed.
The sarne apparatus was used as in Example 1 except only two DY ~och~ mixers in the leading portion of the ir t Kenics section replaced any ~enics elements. The one-i~ch ~illian extruder was run at 145 rpm with temperature settings of 175~C
~rear), 225C (center), and 2S0C (front). The temperature of the three Xenics ~ections was set at 280C. The 28-mm twin screw extruder was run at 130 rpm with the ~ollowing temperatures being recorded: 1 - 140C (rear), 2 - 245C, 3 - 245C,
1~ ~ goo 12.0 "* 2.~2 37~3 63%
*Could not be actually measured but no con~rols were ~hanged during short term of ~hese s~ates; ~herefore, rates probably unchan~ed.
The sarne apparatus was used as in Example 1 except only two DY ~och~ mixers in the leading portion of the ir t Kenics section replaced any ~enics elements. The one-i~ch ~illian extruder was run at 145 rpm with temperature settings of 175~C
~rear), 225C (center), and 2S0C (front). The temperature of the three Xenics ~ections was set at 280C. The 28-mm twin screw extruder was run at 130 rpm with the ~ollowing temperatures being recorded: 1 - 140C (rear), 2 - 245C, 3 - 245C,
4 ~ 250C, 5 - 242C, and die - 215C. Cyclohexyl amine was pumped into the vacuum port of the Killian extruder at a rate of 16.1 ml/min at a pressure of 800 psi. A po~ymer composed of units of methyl methacrylate/styrene/butadiene (70/25/5) was fed to 3~
-the one-inch extruder and a devolatilized final product prod~ced at a rate of 41.9 ~Jmin which contained 2.58% N nitrogen corresponding to 43.2%
N-cyclohexyl imide structure having a Tg of 144C as
-the one-inch extruder and a devolatilized final product prod~ced at a rate of 41.9 ~Jmin which contained 2.58% N nitrogen corresponding to 43.2%
N-cyclohexyl imide structure having a Tg of 144C as
5 determined by DSC.
The same apparatus was used as in Example 1 except ~or the presence of 2DY and 4CY Koch elements in the ~irst Kenics section, 8CY elements in the 10 second, and 2CY elements in the thirdO ~he one inch Rillian extruder was run a~ 144 rpm with temperatures of 250C (rear), 234C (center), and 227C ~fron~).
The three Kenics sec~ions were each set at 280C~
The 28-mm twin screw e~truder was run at 104 rpm wi~h temperatures of 1 - 153C (rear), 2 - 247C, 3 - 275C, 4 - 277Cf 5 - 273C, and die - 284C-Aniline was pumped into the va~uum port o~ the Killian extruder at 9.5 ml/minq The poly~er employed was a copolymer of methyl methacrylate/methacrylic acid (87/13, I.V. in CH2Cl2 - 0.53). Imide product was produced at 35 g/min which contained 1.50% ni~rogen correspondiny to 24.6~ N-cyclohexyl imide of methacrylic acid.
The same apparatus and temperatures were used as in Example 3~ Ammonia was pumped in at the adaptor pla~e at a rate of 5 g/min. ~he pressure was controlled by the die valve to a level of 2000 psi.
Polymer was introduced at a rate of 40 g/min. The polymer employed was a terpolymer having the components methyl methacrylate/styrene/butadiene in a weight ratio of approximately 75/20/5, with an I.~.
in CH2C12 of 0.51. The imidized resin produced contained 4.65% N and had a ~9 of 159C.
:~2 ~
This example demonstrates reaction of cyclohexylamine and methacrylate polymer to ~orm both cyclic imide ~nd anhydride units.
The one-inch Killian ex~ruder was run at 144 rpm with temperature settings of 250C rear, 2~5C
center and front zone. The baffled tubular rea~tor employed comprised the three Renics sections. In section 1, the Kenics baffles were replaced wi~h Koch 10 DY and GY baffles. ~n ~ection 2~ the first Kenics baffle was replaced with a Koch CY baf~le. The sections were ~et at 280C. The valve die and transfer pipe were set at 225C. The 28 mm W-P
extruder had a ~traight through ~rew design with the lS excep~ion of one set of reverse e~ements between ~he regular vacuum ports ~o provide a melt seal and was run at lOB-135 rpm with te~perature settings of 50C
(rear), 200~C (center) and 250C ~die).
A copolymer of methyl methacrylate and ethyl 20 acrylate (95.5~4~5~) with an inherent viscosity oE
0.575 was fed to the 1" extruder at about 37 g/min and cyclohexyl amine pumped in at point A (the vacuum port of the Xillian extruder) or point B (the injection probe), at 900 psi and at abou~ 1~.4 g/min 25 (22 wt %). Imidized polymer was removed for sampling as it existed the baffled tubular reactor (Point I) or after devolatilization in ~he twin screw extruder ~Point II). Resulks were as follows:
~2~
Amine Polymer Addition Sample Imide Anhydride**
Point Point Units* Units 1 A II 37.5 wt ~ 7.5 wt %
2 A I 39.3 5.2 3 B II 37.3 5.6 4 B I 37.3 5.~
*Imide content from nitrogen analysis and infrared spectra **Anhydride content ~rom ~itration and infrared spectra
The same apparatus was used as in Example 1 except ~or the presence of 2DY and 4CY Koch elements in the ~irst Kenics section, 8CY elements in the 10 second, and 2CY elements in the thirdO ~he one inch Rillian extruder was run a~ 144 rpm with temperatures of 250C (rear), 234C (center), and 227C ~fron~).
The three Kenics sec~ions were each set at 280C~
The 28-mm twin screw e~truder was run at 104 rpm wi~h temperatures of 1 - 153C (rear), 2 - 247C, 3 - 275C, 4 - 277Cf 5 - 273C, and die - 284C-Aniline was pumped into the va~uum port o~ the Killian extruder at 9.5 ml/minq The poly~er employed was a copolymer of methyl methacrylate/methacrylic acid (87/13, I.V. in CH2Cl2 - 0.53). Imide product was produced at 35 g/min which contained 1.50% ni~rogen correspondiny to 24.6~ N-cyclohexyl imide of methacrylic acid.
The same apparatus and temperatures were used as in Example 3~ Ammonia was pumped in at the adaptor pla~e at a rate of 5 g/min. ~he pressure was controlled by the die valve to a level of 2000 psi.
Polymer was introduced at a rate of 40 g/min. The polymer employed was a terpolymer having the components methyl methacrylate/styrene/butadiene in a weight ratio of approximately 75/20/5, with an I.~.
in CH2C12 of 0.51. The imidized resin produced contained 4.65% N and had a ~9 of 159C.
:~2 ~
This example demonstrates reaction of cyclohexylamine and methacrylate polymer to ~orm both cyclic imide ~nd anhydride units.
The one-inch Killian ex~ruder was run at 144 rpm with temperature settings of 250C rear, 2~5C
center and front zone. The baffled tubular rea~tor employed comprised the three Renics sections. In section 1, the Kenics baffles were replaced wi~h Koch 10 DY and GY baffles. ~n ~ection 2~ the first Kenics baffle was replaced with a Koch CY baf~le. The sections were ~et at 280C. The valve die and transfer pipe were set at 225C. The 28 mm W-P
extruder had a ~traight through ~rew design with the lS excep~ion of one set of reverse e~ements between ~he regular vacuum ports ~o provide a melt seal and was run at lOB-135 rpm with te~perature settings of 50C
(rear), 200~C (center) and 250C ~die).
A copolymer of methyl methacrylate and ethyl 20 acrylate (95.5~4~5~) with an inherent viscosity oE
0.575 was fed to the 1" extruder at about 37 g/min and cyclohexyl amine pumped in at point A (the vacuum port of the Xillian extruder) or point B (the injection probe), at 900 psi and at abou~ 1~.4 g/min 25 (22 wt %). Imidized polymer was removed for sampling as it existed the baffled tubular reactor (Point I) or after devolatilization in ~he twin screw extruder ~Point II). Resulks were as follows:
~2~
Amine Polymer Addition Sample Imide Anhydride**
Point Point Units* Units 1 A II 37.5 wt ~ 7.5 wt %
2 A I 39.3 5.2 3 B II 37.3 5.6 4 B I 37.3 5.~
*Imide content from nitrogen analysis and infrared spectra **Anhydride content ~rom ~itration and infrared spectra
Claims (5)
1. A process of imidizing a methacrylate or acrylate polymer which comprises, in sequence a) mixing a molten methacrylate or acrylate polymer with ammonia or an aliphatic or aromatic primary amine, b) introducing the molten mixture into a baffled tubular reactor which provides dispersed plug-flow, c) raising the temperature of the mixture inside the tubular reactor to between 200° and 300°C, and d) conducting the molten mixture through the tubular reactor in a time adequate to accomplish imidization but less than necessary for substantial degradation of polymer.
2. The process of Claim 1 wherein in step c), the temperature is 240° to 280°C.
3. The process of Claim 1 or Claim 2 wherein the polymer units are composed of at least 80% by weight methyl methacrylate.
4. The process of Claim 1 or Claim 2 wherein the amine is cyclohexyl amine or ammonia.
5. The process of Claim 1 or Claim 2 wherein the polymer units are composed of at least 80% by weight methyl methacrylate and the amine is cyclohexyl amine or ammonia.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US27843181A | 1981-06-25 | 1981-06-25 | |
| US278,431 | 1981-06-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1210191A true CA1210191A (en) | 1986-08-19 |
Family
ID=23064945
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000405890A Expired CA1210191A (en) | 1981-06-25 | 1982-06-24 | Process for preparing imidized acrylic polymers |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS585306A (en) |
| CA (1) | CA1210191A (en) |
| DE (1) | DE3223847A1 (en) |
| FR (1) | FR2508466B1 (en) |
| GB (1) | GB2101139B (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4689243A (en) * | 1984-02-21 | 1987-08-25 | Mitsubishi Rayon Co., Ltd. | Heat-resistant resin molded article with excellent abrasion resistance and process for producing the same |
| JPS60177034A (en) * | 1984-02-21 | 1985-09-11 | Mitsubishi Rayon Co Ltd | Molded article of heat-resistant resin having improved abrasion resistance and production thereof |
| JPS60190428A (en) * | 1984-03-12 | 1985-09-27 | Mitsubishi Rayon Co Ltd | Molded article of heat-resistant resin having improved abrasion resistance and production thereof |
| CA1247415A (en) * | 1984-03-02 | 1988-12-28 | Isao Sasaki | Light-transmitting fiber |
| JPS60210606A (en) * | 1984-04-03 | 1985-10-23 | Mitsubishi Rayon Co Ltd | Production of methacrylimide-containing polymer excellent in transparency and heat resistance |
| JPS60233106A (en) * | 1984-05-07 | 1985-11-19 | Toray Ind Inc | Optical disk material |
| US4544682A (en) * | 1984-08-24 | 1985-10-01 | The Dow Chemical Company | Polymeric compositions possessing improved flammability resistance |
| JPS6164703A (en) * | 1984-09-05 | 1986-04-03 | Mitsubishi Rayon Co Ltd | Production of methacrylimide-containing polymer excellent in transparency and heat resistance |
| CA1277095C (en) * | 1985-05-01 | 1990-11-27 | Hideaki Makino | Process for preparing methacrylimide-containing polymers |
| US4727117A (en) * | 1985-08-27 | 1988-02-23 | Rohm And Haas Company | Imide polymers |
| CA1279747C (en) * | 1986-01-23 | 1991-01-29 | Hisao Anzai | Methacrylate resin composition and process for its preparation |
| CA1274936A (en) * | 1986-12-25 | 1990-10-02 | Akihiro Watanabe | Random copolymer containing hexagonal imide units, a process for producing the same, and an optical disc substrate made of the random copolymer |
| JPH02123106A (en) * | 1988-10-31 | 1990-05-10 | Mitsubishi Rayon Co Ltd | Production of methacrylamide group-containing polymer |
| US5369189A (en) * | 1989-12-29 | 1994-11-29 | Lucky, Ltd. | Process for the preparation of heat resistant and transparent acrylic resin |
| DE4208916A1 (en) * | 1992-03-20 | 1993-09-23 | Akzo Nv | POLYESTER FIBER AND METHOD FOR THE PRODUCTION THEREOF |
| DE4225044A1 (en) * | 1992-07-29 | 1994-02-03 | Basf Ag | Process for the imidation of polymers based on esters of methacrylic and acrylic acid |
| DE4402666A1 (en) * | 1994-01-29 | 1995-08-03 | Roehm Gmbh | Process for briefly treating a plastic melt with a liquid treatment agent and thermoplastic material produced in the process |
| WO2015030118A1 (en) * | 2013-08-30 | 2015-03-05 | 株式会社日本触媒 | (meth)acrylic resin |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE754657Q (en) * | 1965-11-29 | 1971-01-18 | Kenics Corp | MIXER APPLIANCE |
| CA1106541A (en) * | 1975-11-19 | 1981-08-04 | Richard M. Kopchik | Imidized acrylic polymers |
| US4246374A (en) * | 1979-04-23 | 1981-01-20 | Rohm And Haas Company | Imidized acrylic polymers |
-
1982
- 1982-06-22 FR FR8210867A patent/FR2508466B1/en not_active Expired
- 1982-06-23 GB GB8218197A patent/GB2101139B/en not_active Expired
- 1982-06-24 CA CA000405890A patent/CA1210191A/en not_active Expired
- 1982-06-24 JP JP10771082A patent/JPS585306A/en active Granted
- 1982-06-25 DE DE19823223847 patent/DE3223847A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0345722B2 (en) | 1991-07-12 |
| GB2101139A (en) | 1983-01-12 |
| GB2101139B (en) | 1984-08-01 |
| DE3223847C2 (en) | 1991-08-08 |
| JPS585306A (en) | 1983-01-12 |
| FR2508466B1 (en) | 1986-09-12 |
| FR2508466A1 (en) | 1982-12-31 |
| DE3223847A1 (en) | 1983-03-03 |
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Legal Events
| Date | Code | Title | Description |
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| MKEX | Expiry |