CA1097845A - Free radical polymerization process employing novel substituted alpha amino acetic acid derivatives - Google Patents
Free radical polymerization process employing novel substituted alpha amino acetic acid derivativesInfo
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- CA1097845A CA1097845A CA275,313A CA275313A CA1097845A CA 1097845 A CA1097845 A CA 1097845A CA 275313 A CA275313 A CA 275313A CA 1097845 A CA1097845 A CA 1097845A
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- carboxymethyl
- salt
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- 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
- C08F4/00—Polymerisation catalysts
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract
ABSTRACT OF THE DISCLOSURE
Initiating compounds having the following formula
Initiating compounds having the following formula
Description
FIELD OF Tl113 INVISNTION
This invention concerns the polymerization of ethylenic-ally unsaturated polymerizable monomers susceptible to free radica 1 polymerization. Specifically the invention concerns novel methods for initiating polymerization of such monomers and monomer systems containing inactive initiators which initiators may be activated to polymerize the system.
DESCRIPTION OF TI~E PRIOR ART
Polymerization of ethylenically unsaturated monomers may be initiated by several methods well known to the art. Some of these include the use of high energy electromagnetic radiation such as gamma radiation and x-rays, ultraviolet light radiation, chemical initiators, and thermal means. Many polymerization reactions depend upon the formation of free radicals to cause the initiation of the polymerization. The use of free radical producing agents containing an acetic acid group has been disclos ~d in Chambers' U.S. 3,479,185. The Chambers patent discloses for example the use of a system of N-phenyl glycine or N,N,N',N',-ethylenediamino tetraacetic acid in combination with a
This invention concerns the polymerization of ethylenic-ally unsaturated polymerizable monomers susceptible to free radica 1 polymerization. Specifically the invention concerns novel methods for initiating polymerization of such monomers and monomer systems containing inactive initiators which initiators may be activated to polymerize the system.
DESCRIPTION OF TI~E PRIOR ART
Polymerization of ethylenically unsaturated monomers may be initiated by several methods well known to the art. Some of these include the use of high energy electromagnetic radiation such as gamma radiation and x-rays, ultraviolet light radiation, chemical initiators, and thermal means. Many polymerization reactions depend upon the formation of free radicals to cause the initiation of the polymerization. The use of free radical producing agents containing an acetic acid group has been disclos ~d in Chambers' U.S. 3,479,185. The Chambers patent discloses for example the use of a system of N-phenyl glycine or N,N,N',N',-ethylenediamino tetraacetic acid in combination with a
2,4,5-triphenylimidazolyl dimer as a photopolymerization catalyst.
It has now been discovered however that certain N-substituted aromatic imino monoacetic compounds produce free radicals and provide for excellent and versatile initiators without the additional presence of a dimer.
An additional advantage of the initiators of the present invention is their versatility in that they can cause polymerization in presence or absence of air, oxygen, heat, visibl~
or ultraviolet light. While such sources of radiation energies arel therefore not required, the presence of them as promoters will tend to increase the activity of the initiator and consequently the ratc of polymerization.
~.
1304-1 - 2 - ~;
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. . , . . :
_l ~Oq7845 i SUMM~r~Y OE 'l~llE II~VENTION
According to the invention there is therefore provided a metllod of polymerizing ~ monomer system containing one or more ethylenically unsaturatcd compounds susccptiblc to free radical ¦polymerization which comprises initiating polymcriza~ion ~y ¦contactiny thc systcm with an effectivc amount of a dissolved ¦initiator consistiny essentially of a compound of the formula:
¦ R ~ 2 , l ~ H2COOH
¦where Rl is a substituted or unsubstituted aryl radical and R2 is hydrogen, alkyl or an alkoxy group provided that the ethylenica: ,ly unsaturatc~ compounds do not contain any grou~ witll wllich tl~c acid group of the initiator will preferentially react chemically (as hereinafter deined). Accor~ing to the invention there is als~ \
provide~ a monomer system susceptible to free radical polymerizati n which comprises one or more ethylenically unsaturated monomers and a dissolved initiator consisting essentially of a compound of the formula ~N2 wherein ~ is a substituted or unsubstitu ed Rl- -Cll2COoH
'aryl radical and R2 is hydrogen, alkyl or an alkoxy group, or a sa~ ,t of sai~ compound which salt upon acidification will yield said , compound, provided that the ethylenically unsaturated monomers'do ,~ not contain any yroup with which the acid group of the compound will preferentially react chemically. By aryl is meant a monovalent radical containing an aromatic ring wherein the free valence is on a carbon atom of the aromatic ring.
DESCRIPTION OF T~E INVENTION
-~ An important aspect of the invention requires that the _ initiator must be soluble in at least one phase of the polymerizab: e system. This polymerizable system maybe an emulsion suspension , or solution polymerizable system Often the initiator is soluble .~
B ¦¦
"7845 ~ :
~' .
in the polymerizable monomer or monomers and no additional solvent is required. ~lternatively in a polymerizable system whcre the initiator is not directly soluble in the monomer, the system must comprise a solvent such as for example, water or methanol for the initiator. The term "dissolved initiator" is ~herefore meant to includc initiators dissolved in the polymerizable monomer and initiators dissolved in a solvent. -The initiators which are useful in the practice oE theinvention includc:
~3~4-~ _4_ ~ ' ` ' ' . :
~ ~ - N-CU2COOII N- ( Carboxymethyl~-N-ethylanlline :~ ~ HO- ~ N-CU2COOli N- (carboxymethyl)-4-hydroxyaniline C1- ~ N-CH2COOH N-(carboxymethy1)-4-Chloroani1ine CH30- ~ -N-CH2COOH N-(carboxymethyl)-4-methoxyaniline ~ ( 3 3 ~ -N -CH2COOH N- (oarboxymethyl)-4-t-butylanili~e : ~ -N-CH2COOH N-(carboxymethyl)aniline ~ ~ (l-naphthylimino)acetic acid /~\ /~\
I ~ -N-CH2cOoH
~ J [(l,l'-biphenyl)-4-ylimino]acetic acid ; I Preferred initiators are those wherein R has the formula R wherein R is hydrogen, alkyl, alkoxy, ~1 I phenyl, aralkyl or alkaryl.
j~ R ~ ~ x R R
IHJL:dmc l 04-1 ~ - 5 -~ ~ ^ lOq~45 Tlle initi~tors use~ul in tllo proc~ss of ~ inv~ ion ma be prepared by reacting in an aqueous solution the corresponding arnine component with a slight excess of sodium chloroacetate at elevated temperatures. During the reaction, which is usually complete in 2 hours at reflux, the pH of the reaction mixture is carefully controlled at about 7 by the addition of sodium hydroxid .
After the reaction is completed the product may usually be obtaine as the inactive sodium salt by stripping or alternatively as an active precipitate by acidification such as with hydrochloric acidl In instances where precipitation will not occur after acidificatiol , extraction procedures may be employed to obtain thc product.
Monomer The unsaturated materials which may be polymerized by the practice of this invention are ethylenically unsaturated compounds susceptible to free radical polymerization. These compounds include esters, nitriles and organic halogen compounds which are olefinically unsaturated compounds of both aromatic and aliphatic types. By way of illustration, vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate and other vinyl esters containing as many as 18 or more carbon atoms in the acid moiety, may be polymerized in accordance herewit~ .
Other vinyl derivatives such as vinyl chloride, vinyl fluoride, chlorotrifluoroethylene, tetrafluoroethylcne, butadiene ¦ nitroethylene, methyl vinyl ketone, methyl isopropenyl ketone, but~ 1 ¦vinyl sulfone, vinyl triethoxy silane, ethyl vinyl sulfoxide, styr~ ne ¦nuclear substituted styrenes including o-methyl, m-methyl, ¦p-methyl styrene, divinylbenzene, and other related compounds may ¦also be polymerized in accordance herewith. Vinylidine ¦derivatives, viz., vinylidene chloride, and vinylidene carbonate ¦respond to this polymerization also.
1304-1 ~ - 6 -The acrylates respond particularly well to the tech-niques disclosed herein and the invention extends to include acrylates and methacrylates containin~ up to 18 or more carbon atoms such as ethyl acrylate, propyl acrylate, butyl acrylate, cyclohexo acrylate, cyclohexo methacrylate, isobutyl acrylate, decyl acrylate, dodecyl methacrylate, methyl methacrylate, benzyl acrylate, tetrahydrofurfuryl acrylate, 2-methoxyethyl acrylate, methyl chloroacrylate, pentaerythritol triacrylate, neopentylglyco 1 diacrylate, e~hylene~lycol acrylate phthalate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate and other related compounds such as acrylamide, acrylic acid, methacrylic acid respond to treatment set forth herein.
; Other materials susceptible to the practice hereof include: acrylonitrile, methacrylonitrile, 2-chloroacrylonitrile, and allyl esters, such as the bisallyl biscarbonate ester of diethylene ~lycol.
Copolymers of the aforementioned unsaturated materials may be obtained. Among the copolymers which may be prepared in accordance herewith are: copolymers of butadiene, acrylonitrile, vinyl acetate, vinylidene chloride, methyl acrylate, and divinylbenzene with styrene, and one another. Copolymers of butadiene with styrene, butadiene with acrylonitrile, acrylic acid with acrylamide, vinyl acetate with vinylidene chloride, styrene with methyl acrylate, and styrene with divinylbenzene, are examples of specific copolymers which may be prepared pursuant to this invention. Terpolymers prepared in accordance herewith are often of special utility, such as those derived from butadiene, acrylonitrile, styrene mixtures and other mixtures wherein vinyl acetate, or methyl methacrylate may be components of the terpolyme -s.
PrcEerrcd monomor systoms of thc proscnt invcl-tioll aro those containing water soluble monomers such as acrylamide, diacet ~ne . .
~ 304-1 - 7 -` ~ 10~784S ~
acrylamide, acrylic acid, methacrylic acid; monomcrs such as diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate o~
dimethylaminoethyl acrylate and their derivatives; vinyl monomer systems containing unsaturated maleate and fumarate polyesters;
monomers containing acrylate or methacrylate unsaturation either separately or in combin~tion with comonomers such as styrene, methyl methacrylate, acrylonitrile, vinyl acetate or vinylidene chloride, and latex forming systcms containing butadiene either alone or in combination with copolymerizable vinyl monomers such as styrene, acrylonitrile, vinyl acetate or vinylidene chloride.
The initiators of the invention have different effectiveness in different polymerization media, which may be aqueous or organic in nature. Most of the initiators are soluble in organic media. However, in aqueous media the selection of the best initiator is best determined experimentally. In general the least substituted aromatic monoacetic acid initiator is water soluble. As groups are substituted on the molecules, initiators may lose water solubility. N-phenylglycine was found soluble in aqueous solutions whereas N-carboxymethyl-4-t-butyl aniline was not found soluble in aqueous media.
The ethylenically unsaturated monomers which are polymerizable according to the method of the invention should not contain any gxoup with which the acid group of the initiator will preferentially react chemically. For example, monomer substituent , such as for example, amines, isocyanate or vinyl epoxy groups are highly reactive with the acid groups of the initiator. Such substituents, if present, will derivatise the acid groups to amides or esters. While amine substituents may cause derivation reactions which may be reversible by acidification, substituents '`~
~ 1304-1 - 8 -~ .
i~ S
such as iso~yanate or vinyl epoxy groups will cause irreversible reactions which will perm~nently diminish or terminate the ability of the initiators to generate free radicals. By the phrase "groups with which all the acid groups of the initiator will preferentially react chemically" is therefore meant those highly reacti~e groups which will non-reversibly derivatise all the acid groups of the initiator.
As is well known to those skilled in the art, free radical polymerization refers to those polymerization reactions w ich take place through intermediates having an odd number of electrons and, consequently, an unpaired electron. It is these intermediates which are generally referred to as frce radicals.
The free radicals are normally generated in one or more of a variety of ways such as by the decomposition of a chemical initia or added to the polymerizable mixture or by the application of heat or ionizing radiation to the composition. If the free radical is gene~ated in the presence of an ethylenically unsaturated monomer described above, the radical will add to the double bond with the regeneration of another radical. This radical will, in turn, reac t with another monomer and in the course of the reaction generate another free radical resulting in growth of the polymer chain through the addition of one chain to another. Free radical polymerization is described in detail in, for example, the Encyclopedia of Polymer Science and Technology,Vol. 7, pages 361-~31, Interscience Publishers, 1967, and in the Textbook of Polymer Science, Billmeyer, Interscience Publishers, 1962, pages 262-290.
In addition to growth of the polymer chain, several sid~
reactions can also take place during the course of the polymerization reaction. One of th~se, identified as chain transfer refers to the transfer of an atom from a molecule to a free radical in the reaction mixture. Depending upon the :`
1-04-1 j nature of the other material, this can rc~lt in thc formation of~
additional polymer molecules, the formation of branch ch~in polymers, or in termination of the polymerization reaction on a growing radical chain.
Chain transfer agents do not terminate the polymerization reaction entirely but merely terminate a growing chain and allow the polymerization to start elsewhere. If premature termination of the growing polymer chain occurs, a reduced molecular weight results and other pol~mer properties are achieved. It is~ for this reaso , desirable to include in a free radical polymerization system a chain transfer agent which would function in this manner allowing molecular weight control.
The concentration of the various components utilized in the production of polymers in accordance with the invention may b varied over extremely wide ranges and appears to be not narrowly critical. The concentration of the initiator is dependent on the activity of the initiator used; the type and concentration of othe r components SUCh as solvent and monomer; and promoters such as hea and light. Although a concentration range of from .01 to 2% is economically preferred for optimum monomer conversion, under favorable conditions shown hereafter in the examples, any amounts which are effective ~ay be used eg. initiator concentration of as low as 0.01~ by weight of monomer system and as high as 9~ or mor by weight of monomer system may be used successfully. For exampl in nonaqueous systems the activity of p-toluidine acetic acid is greater than an initiator having an unsubstituted aromative ring such as aniline acetic acid. Hence the concentration of a greatl active initiator may be less than those of less active initiators.
In general in the presence of air, oxygen or other polymerization inhibitors, 1arge~ra~ounts of initiator may bc requircd.
The temperature used in the practice hereof may vary widely and are only limited by the freezing and boiling point of t ' :- ' I
L304~ - 10 -1~7845 pol~merizable system. In aqueous systems the polymerization may be conducted between about 0 and 100C. Nonaqueous media such as styrene or isopropyl methacrylate may allow for polymerization temperatures as high as about 125 C~
Other nonaqueous media may allow for polymerization temper-atures of 200C or higher.
The invention does not exclude the utilization of polymerization inhibitors, accelerators and molecular weight modifiers. Any of these may be employed if so desired.
Inhibitors may include any free radical scavenger.
The polymerization process according to the inven-tion may occur over a wide range of pH. The optimum pH of the polymerizable system will be affected by the stability of the monomer and the solubility and stability of the initiator.
It has also been discovered that the initiators are considerably less active when not substantially in the acid form. The activity of the initiator and thus the rate of polymerization may therefore be regulated by adjustment of pH. As a further advantage, the invention therefore provides for a latent polymerizable system by having the initiators present not in the acid form but as the inactive salt, for example, the inactive sodium salt, or amine salt. Such a latent system may then be activated by the simple adjustment of pH to a point below the neutralization point of the system.
The neutralization point is hereby defined as the pH point of the polymerizable system at which the initi2tor becomes active due to the presence of acid group. Generally the lower the pH of the polymerizable system, the more active the initiator and conversely the higher the pH, the slower the rate of poLymerization will be. It should be noted that the , ~784S
neutralization point of the polymerizable system will vary depending on the specific initiator employed.
A particular advantage of a latent polymerizable system 7 - lla -.,,,, 1~ ,~ , lOq78~S,.
is the ability to polymerize a liquid polymerizable system at any I time in situ merely by the addition of acid to lower the pH of the system. For example, in oil recovery operations, water soluble monomer mixture of so~ium acrylate and acrylamide and an inactive salt of an initiator may be introduced into an oil bearinc3 formation as a low viscosity liquid and subsequently polymerized b r the addition of acid to activate the initiator to produce a highly viscous polymer solution in situ.
The invention also provides for a polymerizable system containing additionally a second free radical polymerization initiating system such as for example, a peroxide system to cause , postcuring.
The invention is further illustrated by the following lexamples in which all parts and percentages are by weight unless otherwise specified.
:,' .
~ ~304~ - 12 -.
'.~. .
r~ 1097845 To a solution of 2 g of acrylamide in 8 ml of distilled water were addsd 20 rng of N-ethyl anilineacetic acid The solution polymerized in 14 hours at room temperature while being exposed to laboratory day light.
To a solution of 2 g of acrylamide in ~ g of methanol were added 100 mg N-phenylglycine. The solution polymerized in 9 ¦
hours at room temperature while being exposed to laboratory day light. A sample not containiny N-phenylglycine, acting as control, did not polymerize.
EX~LE 3 To a solution of 2 g acrylamide in 8 g of methanol were added 50 mg N-phenylglyclne. The solution polymerized in 17 hours at room temperature while being exposed to laboratory day ight. A sample not containing N-phenylglycine, acting as control, id not polymerize.
To a solution of 1 g acrylamide in 4 g of methanol were dded 200 mg N-phenylglycine. The solution was kept at room emperature in the dark. A precipitate indicating polymerization ormed within three days. A sample not containing N-phenylglycine, acting as control, did not polymerize.
E~AMPLE S
To a solution of 1 g acrylamide in 4 g of water were ladded 100 mg N-phenylglycine. The solution was kept at room Itemperature in the dark. The solution polymerized within three days. A sample not containing N~phenylglycine, acting as control, ~` id not polymerize.
HJL:dm ^ 1~97845 E Xl~M~ Ll~ 6 To a solution of 1 g acrylamide in 4 g of water were ~dded 100 mg N-phenylglycine. The pH was adjusted with dilute hydrochloric acid to 1. The solution was kept at room temperature ~n the dark. The solution polymerized within 60 hours. A sample Iot containing N-phenylglycine, ac~ing as control, did not , polymerize.
To a solution in a glass.,contai~er of 2 g acrylamide in 13 g of methanol were added 50 g N-phenylglycine, ! The p}I was ~~~~ ~djusted with dilute hydrochloric acid to 2. After exposure of the uolution to laboratory daylight for 14 hours at room temperature ~olymerization was observed. A sample not containing -phenylglycine, acting as control, did not polymerize.
EX~MPLE 8 To a solution containing 3 grams of acrylamide and l.S
rams of sodium chloride in 5.5 g water, were added 200 m~
~-phenylglycine. The solution was kept at room temperature in the ~ark. The solution polymerized within three days. A sample not ' containing N-phenylglycine, acting as control, did not polymerize.
~he molecular weight of the polyacrylamide produced in the presence of sodium chloride was found to be higher than that produced , ithout the presence of the salt.
I' , ., ~ 130~-l - 14 -:` . .
'
It has now been discovered however that certain N-substituted aromatic imino monoacetic compounds produce free radicals and provide for excellent and versatile initiators without the additional presence of a dimer.
An additional advantage of the initiators of the present invention is their versatility in that they can cause polymerization in presence or absence of air, oxygen, heat, visibl~
or ultraviolet light. While such sources of radiation energies arel therefore not required, the presence of them as promoters will tend to increase the activity of the initiator and consequently the ratc of polymerization.
~.
1304-1 - 2 - ~;
: ,:
. . , . . :
_l ~Oq7845 i SUMM~r~Y OE 'l~llE II~VENTION
According to the invention there is therefore provided a metllod of polymerizing ~ monomer system containing one or more ethylenically unsaturatcd compounds susccptiblc to free radical ¦polymerization which comprises initiating polymcriza~ion ~y ¦contactiny thc systcm with an effectivc amount of a dissolved ¦initiator consistiny essentially of a compound of the formula:
¦ R ~ 2 , l ~ H2COOH
¦where Rl is a substituted or unsubstituted aryl radical and R2 is hydrogen, alkyl or an alkoxy group provided that the ethylenica: ,ly unsaturatc~ compounds do not contain any grou~ witll wllich tl~c acid group of the initiator will preferentially react chemically (as hereinafter deined). Accor~ing to the invention there is als~ \
provide~ a monomer system susceptible to free radical polymerizati n which comprises one or more ethylenically unsaturated monomers and a dissolved initiator consisting essentially of a compound of the formula ~N2 wherein ~ is a substituted or unsubstitu ed Rl- -Cll2COoH
'aryl radical and R2 is hydrogen, alkyl or an alkoxy group, or a sa~ ,t of sai~ compound which salt upon acidification will yield said , compound, provided that the ethylenically unsaturated monomers'do ,~ not contain any yroup with which the acid group of the compound will preferentially react chemically. By aryl is meant a monovalent radical containing an aromatic ring wherein the free valence is on a carbon atom of the aromatic ring.
DESCRIPTION OF T~E INVENTION
-~ An important aspect of the invention requires that the _ initiator must be soluble in at least one phase of the polymerizab: e system. This polymerizable system maybe an emulsion suspension , or solution polymerizable system Often the initiator is soluble .~
B ¦¦
"7845 ~ :
~' .
in the polymerizable monomer or monomers and no additional solvent is required. ~lternatively in a polymerizable system whcre the initiator is not directly soluble in the monomer, the system must comprise a solvent such as for example, water or methanol for the initiator. The term "dissolved initiator" is ~herefore meant to includc initiators dissolved in the polymerizable monomer and initiators dissolved in a solvent. -The initiators which are useful in the practice oE theinvention includc:
~3~4-~ _4_ ~ ' ` ' ' . :
~ ~ - N-CU2COOII N- ( Carboxymethyl~-N-ethylanlline :~ ~ HO- ~ N-CU2COOli N- (carboxymethyl)-4-hydroxyaniline C1- ~ N-CH2COOH N-(carboxymethy1)-4-Chloroani1ine CH30- ~ -N-CH2COOH N-(carboxymethyl)-4-methoxyaniline ~ ( 3 3 ~ -N -CH2COOH N- (oarboxymethyl)-4-t-butylanili~e : ~ -N-CH2COOH N-(carboxymethyl)aniline ~ ~ (l-naphthylimino)acetic acid /~\ /~\
I ~ -N-CH2cOoH
~ J [(l,l'-biphenyl)-4-ylimino]acetic acid ; I Preferred initiators are those wherein R has the formula R wherein R is hydrogen, alkyl, alkoxy, ~1 I phenyl, aralkyl or alkaryl.
j~ R ~ ~ x R R
IHJL:dmc l 04-1 ~ - 5 -~ ~ ^ lOq~45 Tlle initi~tors use~ul in tllo proc~ss of ~ inv~ ion ma be prepared by reacting in an aqueous solution the corresponding arnine component with a slight excess of sodium chloroacetate at elevated temperatures. During the reaction, which is usually complete in 2 hours at reflux, the pH of the reaction mixture is carefully controlled at about 7 by the addition of sodium hydroxid .
After the reaction is completed the product may usually be obtaine as the inactive sodium salt by stripping or alternatively as an active precipitate by acidification such as with hydrochloric acidl In instances where precipitation will not occur after acidificatiol , extraction procedures may be employed to obtain thc product.
Monomer The unsaturated materials which may be polymerized by the practice of this invention are ethylenically unsaturated compounds susceptible to free radical polymerization. These compounds include esters, nitriles and organic halogen compounds which are olefinically unsaturated compounds of both aromatic and aliphatic types. By way of illustration, vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate and other vinyl esters containing as many as 18 or more carbon atoms in the acid moiety, may be polymerized in accordance herewit~ .
Other vinyl derivatives such as vinyl chloride, vinyl fluoride, chlorotrifluoroethylene, tetrafluoroethylcne, butadiene ¦ nitroethylene, methyl vinyl ketone, methyl isopropenyl ketone, but~ 1 ¦vinyl sulfone, vinyl triethoxy silane, ethyl vinyl sulfoxide, styr~ ne ¦nuclear substituted styrenes including o-methyl, m-methyl, ¦p-methyl styrene, divinylbenzene, and other related compounds may ¦also be polymerized in accordance herewith. Vinylidine ¦derivatives, viz., vinylidene chloride, and vinylidene carbonate ¦respond to this polymerization also.
1304-1 ~ - 6 -The acrylates respond particularly well to the tech-niques disclosed herein and the invention extends to include acrylates and methacrylates containin~ up to 18 or more carbon atoms such as ethyl acrylate, propyl acrylate, butyl acrylate, cyclohexo acrylate, cyclohexo methacrylate, isobutyl acrylate, decyl acrylate, dodecyl methacrylate, methyl methacrylate, benzyl acrylate, tetrahydrofurfuryl acrylate, 2-methoxyethyl acrylate, methyl chloroacrylate, pentaerythritol triacrylate, neopentylglyco 1 diacrylate, e~hylene~lycol acrylate phthalate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate and other related compounds such as acrylamide, acrylic acid, methacrylic acid respond to treatment set forth herein.
; Other materials susceptible to the practice hereof include: acrylonitrile, methacrylonitrile, 2-chloroacrylonitrile, and allyl esters, such as the bisallyl biscarbonate ester of diethylene ~lycol.
Copolymers of the aforementioned unsaturated materials may be obtained. Among the copolymers which may be prepared in accordance herewith are: copolymers of butadiene, acrylonitrile, vinyl acetate, vinylidene chloride, methyl acrylate, and divinylbenzene with styrene, and one another. Copolymers of butadiene with styrene, butadiene with acrylonitrile, acrylic acid with acrylamide, vinyl acetate with vinylidene chloride, styrene with methyl acrylate, and styrene with divinylbenzene, are examples of specific copolymers which may be prepared pursuant to this invention. Terpolymers prepared in accordance herewith are often of special utility, such as those derived from butadiene, acrylonitrile, styrene mixtures and other mixtures wherein vinyl acetate, or methyl methacrylate may be components of the terpolyme -s.
PrcEerrcd monomor systoms of thc proscnt invcl-tioll aro those containing water soluble monomers such as acrylamide, diacet ~ne . .
~ 304-1 - 7 -` ~ 10~784S ~
acrylamide, acrylic acid, methacrylic acid; monomcrs such as diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate o~
dimethylaminoethyl acrylate and their derivatives; vinyl monomer systems containing unsaturated maleate and fumarate polyesters;
monomers containing acrylate or methacrylate unsaturation either separately or in combin~tion with comonomers such as styrene, methyl methacrylate, acrylonitrile, vinyl acetate or vinylidene chloride, and latex forming systcms containing butadiene either alone or in combination with copolymerizable vinyl monomers such as styrene, acrylonitrile, vinyl acetate or vinylidene chloride.
The initiators of the invention have different effectiveness in different polymerization media, which may be aqueous or organic in nature. Most of the initiators are soluble in organic media. However, in aqueous media the selection of the best initiator is best determined experimentally. In general the least substituted aromatic monoacetic acid initiator is water soluble. As groups are substituted on the molecules, initiators may lose water solubility. N-phenylglycine was found soluble in aqueous solutions whereas N-carboxymethyl-4-t-butyl aniline was not found soluble in aqueous media.
The ethylenically unsaturated monomers which are polymerizable according to the method of the invention should not contain any gxoup with which the acid group of the initiator will preferentially react chemically. For example, monomer substituent , such as for example, amines, isocyanate or vinyl epoxy groups are highly reactive with the acid groups of the initiator. Such substituents, if present, will derivatise the acid groups to amides or esters. While amine substituents may cause derivation reactions which may be reversible by acidification, substituents '`~
~ 1304-1 - 8 -~ .
i~ S
such as iso~yanate or vinyl epoxy groups will cause irreversible reactions which will perm~nently diminish or terminate the ability of the initiators to generate free radicals. By the phrase "groups with which all the acid groups of the initiator will preferentially react chemically" is therefore meant those highly reacti~e groups which will non-reversibly derivatise all the acid groups of the initiator.
As is well known to those skilled in the art, free radical polymerization refers to those polymerization reactions w ich take place through intermediates having an odd number of electrons and, consequently, an unpaired electron. It is these intermediates which are generally referred to as frce radicals.
The free radicals are normally generated in one or more of a variety of ways such as by the decomposition of a chemical initia or added to the polymerizable mixture or by the application of heat or ionizing radiation to the composition. If the free radical is gene~ated in the presence of an ethylenically unsaturated monomer described above, the radical will add to the double bond with the regeneration of another radical. This radical will, in turn, reac t with another monomer and in the course of the reaction generate another free radical resulting in growth of the polymer chain through the addition of one chain to another. Free radical polymerization is described in detail in, for example, the Encyclopedia of Polymer Science and Technology,Vol. 7, pages 361-~31, Interscience Publishers, 1967, and in the Textbook of Polymer Science, Billmeyer, Interscience Publishers, 1962, pages 262-290.
In addition to growth of the polymer chain, several sid~
reactions can also take place during the course of the polymerization reaction. One of th~se, identified as chain transfer refers to the transfer of an atom from a molecule to a free radical in the reaction mixture. Depending upon the :`
1-04-1 j nature of the other material, this can rc~lt in thc formation of~
additional polymer molecules, the formation of branch ch~in polymers, or in termination of the polymerization reaction on a growing radical chain.
Chain transfer agents do not terminate the polymerization reaction entirely but merely terminate a growing chain and allow the polymerization to start elsewhere. If premature termination of the growing polymer chain occurs, a reduced molecular weight results and other pol~mer properties are achieved. It is~ for this reaso , desirable to include in a free radical polymerization system a chain transfer agent which would function in this manner allowing molecular weight control.
The concentration of the various components utilized in the production of polymers in accordance with the invention may b varied over extremely wide ranges and appears to be not narrowly critical. The concentration of the initiator is dependent on the activity of the initiator used; the type and concentration of othe r components SUCh as solvent and monomer; and promoters such as hea and light. Although a concentration range of from .01 to 2% is economically preferred for optimum monomer conversion, under favorable conditions shown hereafter in the examples, any amounts which are effective ~ay be used eg. initiator concentration of as low as 0.01~ by weight of monomer system and as high as 9~ or mor by weight of monomer system may be used successfully. For exampl in nonaqueous systems the activity of p-toluidine acetic acid is greater than an initiator having an unsubstituted aromative ring such as aniline acetic acid. Hence the concentration of a greatl active initiator may be less than those of less active initiators.
In general in the presence of air, oxygen or other polymerization inhibitors, 1arge~ra~ounts of initiator may bc requircd.
The temperature used in the practice hereof may vary widely and are only limited by the freezing and boiling point of t ' :- ' I
L304~ - 10 -1~7845 pol~merizable system. In aqueous systems the polymerization may be conducted between about 0 and 100C. Nonaqueous media such as styrene or isopropyl methacrylate may allow for polymerization temperatures as high as about 125 C~
Other nonaqueous media may allow for polymerization temper-atures of 200C or higher.
The invention does not exclude the utilization of polymerization inhibitors, accelerators and molecular weight modifiers. Any of these may be employed if so desired.
Inhibitors may include any free radical scavenger.
The polymerization process according to the inven-tion may occur over a wide range of pH. The optimum pH of the polymerizable system will be affected by the stability of the monomer and the solubility and stability of the initiator.
It has also been discovered that the initiators are considerably less active when not substantially in the acid form. The activity of the initiator and thus the rate of polymerization may therefore be regulated by adjustment of pH. As a further advantage, the invention therefore provides for a latent polymerizable system by having the initiators present not in the acid form but as the inactive salt, for example, the inactive sodium salt, or amine salt. Such a latent system may then be activated by the simple adjustment of pH to a point below the neutralization point of the system.
The neutralization point is hereby defined as the pH point of the polymerizable system at which the initi2tor becomes active due to the presence of acid group. Generally the lower the pH of the polymerizable system, the more active the initiator and conversely the higher the pH, the slower the rate of poLymerization will be. It should be noted that the , ~784S
neutralization point of the polymerizable system will vary depending on the specific initiator employed.
A particular advantage of a latent polymerizable system 7 - lla -.,,,, 1~ ,~ , lOq78~S,.
is the ability to polymerize a liquid polymerizable system at any I time in situ merely by the addition of acid to lower the pH of the system. For example, in oil recovery operations, water soluble monomer mixture of so~ium acrylate and acrylamide and an inactive salt of an initiator may be introduced into an oil bearinc3 formation as a low viscosity liquid and subsequently polymerized b r the addition of acid to activate the initiator to produce a highly viscous polymer solution in situ.
The invention also provides for a polymerizable system containing additionally a second free radical polymerization initiating system such as for example, a peroxide system to cause , postcuring.
The invention is further illustrated by the following lexamples in which all parts and percentages are by weight unless otherwise specified.
:,' .
~ ~304~ - 12 -.
'.~. .
r~ 1097845 To a solution of 2 g of acrylamide in 8 ml of distilled water were addsd 20 rng of N-ethyl anilineacetic acid The solution polymerized in 14 hours at room temperature while being exposed to laboratory day light.
To a solution of 2 g of acrylamide in ~ g of methanol were added 100 mg N-phenylglycine. The solution polymerized in 9 ¦
hours at room temperature while being exposed to laboratory day light. A sample not containiny N-phenylglycine, acting as control, did not polymerize.
EX~LE 3 To a solution of 2 g acrylamide in 8 g of methanol were added 50 mg N-phenylglyclne. The solution polymerized in 17 hours at room temperature while being exposed to laboratory day ight. A sample not containing N-phenylglycine, acting as control, id not polymerize.
To a solution of 1 g acrylamide in 4 g of methanol were dded 200 mg N-phenylglycine. The solution was kept at room emperature in the dark. A precipitate indicating polymerization ormed within three days. A sample not containing N-phenylglycine, acting as control, did not polymerize.
E~AMPLE S
To a solution of 1 g acrylamide in 4 g of water were ladded 100 mg N-phenylglycine. The solution was kept at room Itemperature in the dark. The solution polymerized within three days. A sample not containing N~phenylglycine, acting as control, ~` id not polymerize.
HJL:dm ^ 1~97845 E Xl~M~ Ll~ 6 To a solution of 1 g acrylamide in 4 g of water were ~dded 100 mg N-phenylglycine. The pH was adjusted with dilute hydrochloric acid to 1. The solution was kept at room temperature ~n the dark. The solution polymerized within 60 hours. A sample Iot containing N-phenylglycine, ac~ing as control, did not , polymerize.
To a solution in a glass.,contai~er of 2 g acrylamide in 13 g of methanol were added 50 g N-phenylglycine, ! The p}I was ~~~~ ~djusted with dilute hydrochloric acid to 2. After exposure of the uolution to laboratory daylight for 14 hours at room temperature ~olymerization was observed. A sample not containing -phenylglycine, acting as control, did not polymerize.
EX~MPLE 8 To a solution containing 3 grams of acrylamide and l.S
rams of sodium chloride in 5.5 g water, were added 200 m~
~-phenylglycine. The solution was kept at room temperature in the ~ark. The solution polymerized within three days. A sample not ' containing N-phenylglycine, acting as control, did not polymerize.
~he molecular weight of the polyacrylamide produced in the presence of sodium chloride was found to be higher than that produced , ithout the presence of the salt.
I' , ., ~ 130~-l - 14 -:` . .
'
Claims (8)
1. A monomer system susceptible to free radical polymerization which comprises one or more ethylenically un-saturated monomers and a dissolved initiator selected from the group consisting of N-(Carboxymethyl)-N-ethylaniline N-(carboxymethyl)-4-hydroxyaniline N-(carboxymethyl)-4-chloroaniline N- (carboxymethyl)-4-methoxyaniline N-(carboxymethyl)-4-t-butylaniline N-(carboxymethyl)aniline (1-naphthylimino)acetic acid [(1,1'-biphenyl)-4-ylimino]acetic acid or a salt of said compound which will yield the compound upon acidification, provided that the ethylenically unsaturated monomers do not contain any group with which the acid group of the initiator compound will preferentially react chemically
2 A monomer system as claimed in Claim 1 wherein the salt of the compound is an alkali metal salt
3. A monomer system as claimed in Claim l wherein the salt of the compound is an amine salt
4. A monomer system as claimed in Claim 1 wherein the monomers are selected from class consisting of acrylamide, acrylic acid, methacrylic acid, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, maleate or fumarate polyester, butadiene, styrene, methyl methacrylate, acrylonitrile, vinyl acetate and vinylidene chloride,
5. A method of polymerizing a monomer system con-taining one or more ethylenically unsaturated monomers sus-ceptible to free radical polymerization which comprises ini-tiating polymerization by contacting the system with an effect-ive amount of dissolved initiator selected from the group consisting of N-(Carboxymethyl)-N-ethylaniline N-(carboxymethyl)-4-hydroxyaniline N-(carboxymethyl)-4-chloroaniline N-(carboxymethyl)-4-methoxyaniline N-(carboxymethyl)-4-t-butylaniline N-(carboxymethyl)aniline (1-naphthylimino)acetic acid [(1,1'-biphenyl)-4-ylimino]acetic acid or a salt of said compound which will yield the compound upon acidification provided that the ethylenically unsaturated compounds do not contain any group with which the acid group of the initiator will preferentially react chemically
6. A method of polymerizing a monomer system as claimed in Claim 5 wherein the salt is an alkali metal salt acid.
7. A method of polymerizing a monomer system as claimed in Claim 5 wherein the salt is an amine salt
8. A method as claimed in Claim 5 wherein the monomers are selected from class consisting of acrylamide, acrylic acid, methacrylic acid, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, maleate, or fumarate polyester, butadiene, styrene, methyl methacrylate, acrylonitrile, vinyl acetate and vinylidene chloride.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US673,539 | 1976-04-05 | ||
| US05/673,938 US4058656A (en) | 1976-04-05 | 1976-04-05 | Free radical polymerization process employing substituted amino acetic acid derivatives |
| US05/673,539 US4095019A (en) | 1976-04-05 | 1976-04-05 | Free radical polymerization process utilizing novel initiators |
| US673,938 | 1991-03-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1097845A true CA1097845A (en) | 1981-03-17 |
Family
ID=27100962
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA275,313A Expired CA1097845A (en) | 1976-04-05 | 1977-04-01 | Free radical polymerization process employing novel substituted alpha amino acetic acid derivatives |
| CA275,314A Expired CA1097846A (en) | 1976-04-05 | 1977-04-01 | Free radical polymerization process employing novel substituted alpha amino acetic acid derivatives |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA275,314A Expired CA1097846A (en) | 1976-04-05 | 1977-04-01 | Free radical polymerization process employing novel substituted alpha amino acetic acid derivatives |
Country Status (12)
| Country | Link |
|---|---|
| JP (1) | JPS52121086A (en) |
| AU (1) | AU509532B2 (en) |
| BR (1) | BR7702112A (en) |
| CA (2) | CA1097845A (en) |
| CH (1) | CH610912A5 (en) |
| DE (1) | DE2715328A1 (en) |
| FR (1) | FR2347384A1 (en) |
| GB (1) | GB1568445A (en) |
| IT (1) | IT1116418B (en) |
| MX (1) | MX150556A (en) |
| NL (1) | NL7703677A (en) |
| SE (1) | SE7703931L (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04161143A (en) * | 1990-10-25 | 1992-06-04 | Masahiko Shimizu | Physical exercise recorder |
| US5324747A (en) * | 1992-07-15 | 1994-06-28 | Hoffmann-La Roche Inc. | N-substituted anilines, inhibitors of phospholipases A2 |
| CN114292354B (en) * | 2021-11-01 | 2023-06-16 | 深圳市森若新材科技有限公司 | Polymer phase change material applicable to cold accumulation of air conditioner |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3746611A (en) * | 1970-10-21 | 1973-07-17 | Union Carbide Corp | Silyl acyl peroxide and acyl peroxy polysiloxane binders |
-
1977
- 1977-03-30 GB GB13447/77A patent/GB1568445A/en not_active Expired
- 1977-03-30 IT IT48730/77A patent/IT1116418B/en active
- 1977-03-31 AU AU23840/77A patent/AU509532B2/en not_active Expired
- 1977-04-01 CA CA275,313A patent/CA1097845A/en not_active Expired
- 1977-04-01 DE DE19772715328 patent/DE2715328A1/en active Granted
- 1977-04-01 CA CA275,314A patent/CA1097846A/en not_active Expired
- 1977-04-04 BR BR7702112A patent/BR7702112A/en unknown
- 1977-04-04 NL NL7703677A patent/NL7703677A/en not_active Application Discontinuation
- 1977-04-04 SE SE7703931A patent/SE7703931L/en unknown
- 1977-04-04 MX MX168624A patent/MX150556A/en unknown
- 1977-04-05 FR FR7710315A patent/FR2347384A1/en active Granted
- 1977-04-05 JP JP3894177A patent/JPS52121086A/en active Granted
- 1977-04-05 CH CH428077A patent/CH610912A5/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| DE2715328C2 (en) | 1987-08-20 |
| SE7703931L (en) | 1977-10-06 |
| AU2384077A (en) | 1978-10-05 |
| FR2347384A1 (en) | 1977-11-04 |
| CA1097846A (en) | 1981-03-17 |
| DE2715328A1 (en) | 1977-10-27 |
| JPS6154802B2 (en) | 1986-11-25 |
| JPS52121086A (en) | 1977-10-12 |
| GB1568445A (en) | 1980-05-29 |
| FR2347384B1 (en) | 1981-02-13 |
| BR7702112A (en) | 1978-01-10 |
| IT1116418B (en) | 1986-02-10 |
| AU509532B2 (en) | 1980-05-15 |
| NL7703677A (en) | 1977-10-07 |
| CH610912A5 (en) | 1979-05-15 |
| MX150556A (en) | 1984-05-30 |
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