WO1994015975A1 - Copolymers of epoxybutadiene and imidized derivatives of maleic anhydride - Google Patents
Copolymers of epoxybutadiene and imidized derivatives of maleic anhydride Download PDFInfo
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- WO1994015975A1 WO1994015975A1 PCT/US1993/011604 US9311604W WO9415975A1 WO 1994015975 A1 WO1994015975 A1 WO 1994015975A1 US 9311604 W US9311604 W US 9311604W WO 9415975 A1 WO9415975 A1 WO 9415975A1
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- maleic anhydride
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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
- C08F8/00—Chemical modification by after-treatment
- C08F8/48—Isomerisation; Cyclisation
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3209—Epoxy compounds containing three or more epoxy groups obtained by polymerisation of unsaturated mono-epoxy compounds
Abstract
Copolymers are produced when a 3,4-epoxy-1-butene monomer is copolymerized with an imidized maleic anhydride (maleimide) monomer in the presence of a free radical initiator. The copolymerization comprises both 1,2-propagation and 1,4-propagation of 3,4-epoxy-1-butene. Alternately, a maleamic acid or maleimide functionality may be introduced into a copolymer containing 3,4-epoxy-1-butene and maleic anhydride by introducing a primary amine into the reaction mixture. The structure and composition of the product copolymer are controlled by both the sequence and conditions of the reaction. Products of this invention can be cast as clear films and can also be used as reactive polymers.
Description
COPOLYMERS OF EPOXYBUTADIENE AND IMIDIZED DERIVATIVES OF MALEIC ANHYDRIDE
FIELD OF THE INVENTION This invention relates to copolymers and to processes for their formation.
BACKGROUND OF THE INVENTION U.S. Patents 5,013,806; 5,071,930; 5,071,931; and 5,071,932 (issued to Blevins and Turner in 1991) disclose copolymers of 3,4-epoxy—1—butenes and maleic anhydrides. Other than the compounds and processes described in these patents, no other known reference discloses copolymers of 3,4—epoxy—1—butene with maleic anhydride or its derivatives. It is known that polymers containing maleic anhydride may be imidized to provide maleamic acids and that various chemical means are available to facilitate the ring closure of maleamic acids to form maleimides. However, we are aware of no references involving the polymerization of imidized derivatives of maleic anhydride with 3,4—epoxy—1—butenes.
While the copolymers of the above cited patents are useful, it would be desirable to have copolymers with improved properties such as greater resistance to moisture and hydrolysis.
SUMMARY OF THE INVENTION This invention provides a method of making novel copolymers from (i) 3,4—epoxy—1—butene, a difunctional reactant monomer, and (ii) an imidized maleic anhydride. The invention also provides the novel copolymers derived thereby.
The invention is a process for the preparation of a copolymer, comprising:
(A) contacting (i) a 3 ,4—epoxy—1—butene monomer reactant with (ii) a maleic anhydride reactant, in the presence of a free radical initiator, at a temperature from —10°C to 180°C; and
(B) contacting the product of (A) with a primary amine reactant.
The process of the present invention provides several advantages. For example, the process can produce polymers at mild reaction temperatures and pressures thereby avoiding high energy consumption. Further, the process can produce polymers which are soluble in organic solvents, alcohols and water and, hence, need not be melted prior to use as coating materials. The convenience of using water as a solvent also has environmental and regulatory benefits. Additionally, the process of the present invention avoids the more rigorous requirements of anionic polymerization procedures.
The product of the method described above is a copolymer having repeating units of the formula:
R represents hydrogen, alkyl, aryl, substituted aryl, or an alicyclic hydrocarbon having from 1 to 20 carbon atoms; each R1 independently represents hydrogen, chlorine, bromine, fluorine, cyano or a lower primary or secondary alkyl of 1 to 4 carbon atoms; each R2 independently represents hydrogen or alkyl having 1 to 4 carbon atoms; and
(a + b) is approximately equal to (c+d+e) ; may be zero, and either of c or e, but not both, may be zero; a represents the molar per cent of Formula I in the 1,2— isomeric form, b represents the molar per cent of Formula I in the
1,4— isomeric form, c represents the molar per cent of Formula III, d represents the molar per cent of Formula II, and e represents the molar per cent of Formula IV, in the copolymer.
Preferably, R is alkyl from 1 to 4 carbons, (e.g. methyl, ethyl, t—butyl) benzyl or cyclohexyl, R1 is hydrogen or chlorine, and R2 is hydrogen. Preferably, (a+b) is equal to 50 mole per cent and (c+d+e) is equal to 50 mole per cent of the entire polymer.
As mentioned above, the copolymer has alternating units of Formula I and Formula II or its derivatives, so that for each mole portion of 3,4—epoxy—1—butene, there is one mole portion of maleic anhydride and its imidized derivatives. In other words, in the above formula,
(a+b) » (c+d+e) . Also, (d)=0 where 100% of Formula II was imidized in the reaction. Similarly, (e)=0 where 100% of Formula IV was (optionally) cyclized in the reaction. When Formula IV is not cyclized, c=0. Thus, in the copolymer of the invention d can be zero, and either c or e, but not both, may optionally also be zero.
The copolymers of the invention are considerably more resistant to moisture and hydrolysis than are the copolymers reported by Blevins and Turner. Accordingly, such copolymers represent new compositions of matter and provide significant advance over the known art.
These results were unexpected; first, because 3,4—epoxy—1—butene is relatively unknown and it was
uncertain how it would react in a polymerization process; and second, because some reactants in the copolymer (for example, maleimide) are known to homopolymerize very readily, and so it was surprising that the useful copolymers of the invention were obtained.
The products of this invention are useful alone or as chemical intermediates. They may be incorporated into formulations as binders, dispersing agents, co patibilizerε and the like. The copolymers are resinous materials which are valuable for use in plastics, coatings, laminating, adhesives, paper and cloth treatments and other arts. The products of this invention may also be cast as films. Some modifications of this invention may be used as reactive polymers or crosslinking agents.
DETAILS OF THE INVENTION The 3,4—epoxy—1—butene monomer reactant has the formula:
(b) The maleic anhydride monomer reactant has the formula:
Formula II
wherein R1 independently represents hydrogen, chlorine, bromine, fluorine, cyano or a lower primary or secondary alkyl of 1 to 4 carbon atoms.
The resulting copolymer is then reacted with a primary amine to produce a copolymer product having repeating units of Formula IV:
Optionally, units of Formula IV may be cyclized chemically (for example, by using acetic anhydride and pyridine) or thermally to produce units within the copolymer having the Formula III:
The reaction takes place in the presence of a free radical initiator. As described above, a 3,4—epoxy—1—butene reactant
(Formula I) is first polymerized with a maleic anhydride reactant (Formula II) , and subsequently an imide functionality is introduced by the addition of an appropriate primary amine into the reaction mixture. Alternatively, the imide functionality can be added onto a preformed copolymer wherein the maleic anhydride—3,4— epoxy—1—butene copolymer is recovered from the mixture and later redissolved in an appropriate solvent such as
2—butanone, tetrahydrofuran, or cyclohexanone. The imide functionality is subsequently formed by amine addition and optionally the amine may subsequently be cyclized either chemically or thermally as is well known in the art.
The 3,4—epoxy—1—butene repeating unit may be in either the 1,2— or 1,4—isomeric form:
"1,2-" "1,4-" Formula IA Formula IB wherein R2 is as defined above.
A skilled practitioner will recognize that the anhydride of Formula II is easily hydrolyzed and thus, if water is introduced into the system containing the polymer (for example, during the reaction process) , the copolymer products of the invention may exist in hydrolyzed form (Formula V below) :
Additionally, it is recognized that if water is present during the polymerization process, a ring- opening reaction may occur on the 3,4—epoxy—1—butene, which would lead to an ester linkage between it and the maleic anhydride. The resulting ester derivative would be present in the product polymer.
Exemplary compounds of Formula III include N—methylmaleimide, N—ethylmaleimide, N—propylmaleimide, N—isopropylmaleimide, N—butylmaleimide, N—sec—butyl— maleimide, N—t—butylmaleimide, N—pentylmaleimide, N—decylmaleimide, N—dodecylmaleimide, N—cyclohexyl— maleimide, N—phenylmaleimide, N—benzylmaleimide, N—(4— methyIpheny1)maleimide, N—(3—methyIpheny1)maleimide, N—(2—methyIpheny1)maleimide, N—(3,5—dimethyIpheny1)male¬ imide, N—(4—iodophenyl)maleimide, N—(4—acetoxyphenyl)— maleimide, and N—naphthylmaleimide.
Suitable amines for reacting with the anhydride functionality enchained in the copolymers resulting from step (A) of the method of the invention, include: methylamine, ethylamine, propylamine, isopropylamine, butylamine, butylamine, butylamine, pentylamine, decylamine, dodecylamine, octadecylamine, cyclo— hexylamine, phenylamine, benzylamine, 4—methyIpheny1— amine, 3—methyIphenylamine, 2—methyIpheny1) amine, 3 , 5—dimethyIphenylamine, 4—iodophenylamine, N—naphthylamine, and 4—acetoxyphenylamine. Amines which are alkyl, aryl, or substituted aryl are preferred.
The polymerization process may be carried out with or without adding a solvent or by conventional emulsion polymerization procedures. Non—reactive diluent solvent systems include both polar and non—polar chemicals such as toluene, heptane, ethyl ether, tetrahydrofuran, and others. Also, two or more solvents may be combined. The purpose of the solvent system is to permit contact of the monomers and facilitate polymerization. Solvents may also be selected for reasons not directly related to the polymerization step, such as ease of recovery or simplified isolation procedures. Additionally, the solvent may be chosen based on later uses for the product polymer, where the polymer is not isolated but
used directly from the reaction mixture. As such, the choice of the solvent is unlimited as long as it does not inhibit, interfere with or otherwise have a deleterious impact on the polymerization, isolation or later applications. The choice of solvent and the monomer concentration may influence and alter the speed and yield of the polymerization process, as well as the molecular weight of the product polymer. Other factors such as economics, ease of recovery and toxicity may influence the choice of diluent solvents.
As mentioned above, it is not necessary to add solvent to the reaction mixture. Instead, the 3,4—epoxy—1—butene monomer may be used in such amounts, preferably stoichiometric or in excess of the anhydride, that it acts as both a diluent solvent and a reactant.
3,4—Epoxy—1—butene is liquid at the reaction temperature and may be used to dissolve enough of the anhydride reactant and initiator to permit polymerization to occur. This approach could simplify both the reaction and the recovery procedures.
In all embodiments of the invention, it is not necessary that the reactants be added to the reaction zone in the ratio expected or desired in the copolymer product; an excess of either reactant can be employed. There is no real upper limit on the amount of excess employed; this being defined by such secondary considerations as size of the reaction vessel, cost of the reactants, ease of separation of the starting materials from products, etc. In general, one uses from 0.5 to 5.0 moles of one reactant per mole of the other. However, it is to be understood that the composition of the polymer product is relatively insensitive to the ratio of reactants in the feed composition.
The polymerization reaction is initiated by a free radical generating composition. Such initiators may be selected from a wide variety of materials which are known to cause polymerization of ethylenically unsaturated monomers. These materials include, but are not limited to azobisisobutyronitrile (AIBN) , peroxides, azides, redox initiators, and similar compounds familiar to those skilled in the art. The amount of initiator employed is not critical. One employs enough initiator to achieve the desired result. Generally speaking, the amount of initiator is from 0.1 to 10 weight percent of any individual monomer in the reaction mixture. A skilled practitioner will recognize that more or less initiator may be used to obtain polymers of molecular weights somewhat outside the ranges stated in the claims.
If a redox initiator is used, a reaction temperature somewhat below the temperature used with free radical initiation may be desired. Thus, for example, redox initiators can be employed at room temperature or below. Similar processes of polymerization are also described in U.S. Patents 5,071,930; 5,071,931, 5,071,932 and 5,013,806.
The temperature of the polymerization reaction may be varied over a wide range including temperatures over the boiling point of any of the reaction monomers or solvents when done under pressure. Several commercial processes for the manufacture of maleic anhydride copolymers, discussed by B.M. Culbertson, Encyclopedia of Polymer Science and Engineering. Vol. 9, pp. 225—294 (1987) , involve the use of pressure reactions to increase molecular weight. In most cases the polymerization temperature will be within the range of —10 to 180 degrees centigrade, more particularly within
the range of 15 to 120 degrees, depending upon the initiator system employed and other influencing factors. For example, most redox initiators are employed at room temperature or below, whereas free—radical initiators require higher temperatures. The reaction is allowed to continue for a time sufficient to allow the copolymer product to form. The process time can be seconds, or up to 48 hours, depending on whether the process is continuous or whether an intermediate is first recovered.
The formula of the copolymer derived by the method of the invention has already been described above. Generally the copolymer has a number average molecular weight of 500 to 250,000. The specific structure of an individual copolymer is determined by the constituent monomeric units and by the degree of imidization and/or cyclization carried out during the process of making it.
For example, units derived from Formula I do not homopolymerize. Similarly, units derived from Formula II do not homopolymerize. Hence, the process of this invention proceeds by an alternating polymeriza¬ tion, and the units derived from each reactant alternate along the polymer chain in a fashion illustrated by
-II-I-II-I-II-I- wherein II is maleic anhydride (Formula II) or a unit derived therefrom and I is a unit derived from 3,4—epoxy—1—butene (Formula I).
Also, when Formula II in the copolymer is imidized (Step (B) in the method of the invention) to provide Formula IV, depending on the degree of imidization carried out, either some or all of Formula II may be imidized to Formula IV. Hence, the product copolymer may contain units of both Formulas II and IV.
Similarly, any fractional amount of Formula IV may optionally be cyclized to provide Formula III (maleimide) and hence, the copolymer product may contain both Formulas III and IV. Representative polymerizations of 3,4—epoxy—1— butene and imidized derivatives of maleic anhydride follow.
EXAMPLES Example 1: In a dry glove box under helium, 3 ,4—epoxy—1—butene
(0.70 gram, 10 mmol), N-methyl maleimide (1.11 gram, 10 mmol), azobisisobutyronitrile (AIBN) (0.032 gram, 0.2 mmol) and 3.62 grams of dry toluene were combined in a Claisen bottle with a magnetic stirrer and then sealed. The reaction mixture was heated with stirring in an oil bath at 70°C for 20 hours. The product polymer rapidly precipitated out of solution and coated the walls of the Claisen bottle during the reaction. The reaction mixture was diluted with 5 grams dimethylsulfoxide and 5 grams of tetrahydrofuran (THF) and precipitated into ethyl ether. The solid product was collected using suction filtration and dried under vacuum at 40°C for 20 hours. Yield was 1.02 gram, 56% theory. Size Exclusion Chromatography (SEC) gave number average molecular weight (Mn) = 1280, size average molecular weight (Mw) = 1770, Mw/Mn = 1.38. Nuclear magnetic resonance (NMR) indicated both 1,2— and 1,4—propagation of epoxybutene. The methyl group of the maleimide was present. Example 2: Example 1 was repeated using THF instead of
2—butanone as the solvent. Yield was 0.60 gram, 33% theory. Mn = 723, Mw = 835, Mw Mn ■= 1.15. NMR indicated both 1,2— and 1,4—propagation of epoxybutene. The methyl group of the maleimide was present.
Example 3:
In a dry glove box under helium, 3,4—epoxy—1—butene (2.10 gram, 30 mmol), N— ethyl maleimide (1.11 gram, 10 mmol), and AIBN (0.032 gram, 0.2 mmol) were combined in a Claisen bottle with a magnetic stirrer and then sealed. The reaction mixture was heated with stirring in an oil bath at 70°C for 20 hours. The reaction mixture was diluted with 5 grams of THF and 5 grams of dimethylsulfoxide and precipitated into ethyl ether. The solid product was collected using suction filtration and dried under vacuum at 40°C for 20 hours. Yield was 1.05 gram, 33% theory. Mn = 2520, Mw = 5370, Mw/Ηn = 2.14. NMR indicated both 1,2— and 1,4—propagation of epoxybutene. The methyl group of the maleimide was also present.
EXAMPLE 4:
In a dry glove box under helium, 3,4—epoxy—1—butene (0.56 gram, 8 mmol), maleic anhydride (0.784 gram, 8 mmol), 4.03 grams of anhydrous 2—butanone and AIBN (0.013 gram, 0.08 mmol) were combined in a Claisen bottle with a magnetic stirrer and then sealed. The reaction mixture was heated with stirring in an oil bath at 70°C for 24 hours. The reaction mixture was diluted with 5 grams of 2—butanone and precipitated into ethyl ether. The solid product was collected using suction filtration and dried under vacuum at 50°C for 20 hours. Yield was .32 gram, 24% theory. Mn = 1690, Mw = 4730, Mw/Mn = 2.80. NMR indicated both 1,2— and 1,4-propaga- tion of epoxybutene. The peaks consistent with the incorporation of 2,2-dimethyl—4—vinyl—1,3—dioxolane (formed in situ) are present.
The invention has been described in detail with particular reference to preferred embodiments thereof.
but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
Claims
1. A copolymer comprising polmerized repeating monomeric units of (a) 3,4—epoxy—1—butene, and (b) an imidized derivative of maleic anhydride.
2. A copolymer having repeating units of the formula:
R represents hydrogen, alkyl, aryl, substituted aryl, or an alicyclic hydrocarbon having from 1 to 20 carbon atoms; each R1 independently represents hydrogen, chlorine, bromine, fluorine, cyano or a lower primary or secondary alkyl of 1 to 4 carbon atoms; each R2 independently represents hydrogen or alkyl having 1 to 4 carbon atoms, such that the total number of carbon atoms in R2 is up to 8; and
(a + b) is approximately equal to (c+d+e) ; d is optionally equal to zero, and either of c or e, but not both, may optionally be equal to zero.
3. A copolymer according to claim 2 wherein (a+b) is equal to 50 mole per cent and (c+d+e) is equal to 50 mole per cent of the entire copolymer.
4. A copolymer according to claim 1 having a number average molecular weight of 500 to 250,000.
5. A copolymer according to claim 2 wherein R is hydrogen, methyl, ethyl, t—butyl, or benzyl.
6. A copolymer according to claim 2 wherein each R1 represents chlorine or hydrogen.
7. A copolymer according to claim 2, wherein each R2 represents hydrogen.
8. A process for the preparation of the copolymer defined in claim 1, comprising:
(A) contacting (i) a butadiene onoepoxide reactant with (ii) a maleic anhydride reactant, each having up to 12 carbon atoms, said contact being in the presence of a free radical initiator, at a temperature from —10°C to 180°C; and
(B) contacting the product of (A) with a primary amine reactant.
9. A process according to claim 7 wherein the product of (B) is cyclized.
10. A process according to claim 7 conducted in a non polar or ether solvent, or in the absence of added solvent.
11. A process according to claim 7, wherein the primary amine is alkyl, aryl, or substituted aryl.
12. The process described in claim 7 wherein the free radical initiator is a peroxide or azobisisobutyronitrile.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US99820292A | 1992-12-30 | 1992-12-30 | |
| US998,202 | 1992-12-30 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3453246A (en) * | 1966-03-14 | 1969-07-01 | Gulf Research Development Co | Thermosettable composition composed of a polyanhydride and a mono-oxirane compound and method of producing |
| EP0154177A2 (en) * | 1984-02-17 | 1985-09-11 | Bayer Ag | Copolymers based on maleic anhydride and alpha-, beta-unsaturated compounds, process for their manufacture and their use as paraffin inhibitors |
| EP0156210A2 (en) * | 1984-03-08 | 1985-10-02 | Dainippon Ink And Chemicals, Inc. | Curable resin compositions based on tertiary amino group-containing vinyl polymers |
| EP0255802A2 (en) * | 1986-08-06 | 1988-02-10 | Ciba-Geigy Ag | Copolymers from N-hydroxyphenyl maleimide derivatives and allylic compounds |
| US5013806A (en) * | 1990-03-23 | 1991-05-07 | Eastman Kodak Company | Butadiene monoepoxide/maleic anhydride copolymers |
-
1993
- 1993-12-03 WO PCT/US1993/011604 patent/WO1994015975A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3453246A (en) * | 1966-03-14 | 1969-07-01 | Gulf Research Development Co | Thermosettable composition composed of a polyanhydride and a mono-oxirane compound and method of producing |
| EP0154177A2 (en) * | 1984-02-17 | 1985-09-11 | Bayer Ag | Copolymers based on maleic anhydride and alpha-, beta-unsaturated compounds, process for their manufacture and their use as paraffin inhibitors |
| EP0156210A2 (en) * | 1984-03-08 | 1985-10-02 | Dainippon Ink And Chemicals, Inc. | Curable resin compositions based on tertiary amino group-containing vinyl polymers |
| EP0255802A2 (en) * | 1986-08-06 | 1988-02-10 | Ciba-Geigy Ag | Copolymers from N-hydroxyphenyl maleimide derivatives and allylic compounds |
| US5013806A (en) * | 1990-03-23 | 1991-05-07 | Eastman Kodak Company | Butadiene monoepoxide/maleic anhydride copolymers |
| WO1991014720A1 (en) * | 1990-03-23 | 1991-10-03 | Eastman Kodak Company | Butadiene monoepoxide/maleic anhydride copolymers |
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