CA1299302C - Retro diels alder assisted polymers grafting process - Google Patents
Retro diels alder assisted polymers grafting processInfo
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- CA1299302C CA1299302C CA000558349A CA558349A CA1299302C CA 1299302 C CA1299302 C CA 1299302C CA 000558349 A CA000558349 A CA 000558349A CA 558349 A CA558349 A CA 558349A CA 1299302 C CA1299302 C CA 1299302C
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- diels alder
- alder adduct
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Abstract
ABSTRACT
A polymer grafting process in which a Diels Alder adduct is mixed with a polyolefin or vinyl polymer substrate and thermally decomposed to form an ethylenically unsaturated monomer which grafts onto the polymer substrate. The monomer conforms generally to the formula R1R2C=CHR3 in which R1 is hydrogen, methyl or ethyl, R2 is hydrogen, methyl, ethyl or vinyl and R3 is hydroxyl, carboxyl, cyanc, formyl, acetyl or propanoyl. The Diels Alder adduct substantially decomposes at a temperature of 120 to 300°C, but does not substantially decompose below about 120°C. The polymer substrate is preferably high-density polyethylene, low density polyethylene, linear low density polyethylene, ethylene-propylene rubber, propylene, polystyrene or styrene-butadiene block copolymers. The grafting is induced by, for example, heat, catalyst and/or high shear conditions.
Optionally, the polymer mixture is devolatilized to 32,836-F
remove any unreacted Diels Alder adduct and decomposition products thereof.
32,836-F
A polymer grafting process in which a Diels Alder adduct is mixed with a polyolefin or vinyl polymer substrate and thermally decomposed to form an ethylenically unsaturated monomer which grafts onto the polymer substrate. The monomer conforms generally to the formula R1R2C=CHR3 in which R1 is hydrogen, methyl or ethyl, R2 is hydrogen, methyl, ethyl or vinyl and R3 is hydroxyl, carboxyl, cyanc, formyl, acetyl or propanoyl. The Diels Alder adduct substantially decomposes at a temperature of 120 to 300°C, but does not substantially decompose below about 120°C. The polymer substrate is preferably high-density polyethylene, low density polyethylene, linear low density polyethylene, ethylene-propylene rubber, propylene, polystyrene or styrene-butadiene block copolymers. The grafting is induced by, for example, heat, catalyst and/or high shear conditions.
Optionally, the polymer mixture is devolatilized to 32,836-F
remove any unreacted Diels Alder adduct and decomposition products thereof.
32,836-F
Description
DIELS ALDER ASSISTED
POLYMER GRAFTING PROCESS
This invention relates to a method o~ grafting an ethylenically unsaturated monomer onto a polyolefin or polyvinyl polymer substrate and particularly to such a method in which a Diels Alder adduct of the monomer to be grafted is employed to provide the source of the ethylenically unsaturated monomer through a retro Diels Alder mechanism.
The grafting of ethylenically unsaturated monomers onto a molten polymer substrate with or without a free radical initiator is well known. For example 9 methods of grafting monomers such as maleic anhydride onto polyethylene in an extruder are described in U. S. Patents 3,882,194 and 3,873,643.
In many applications~ however~ the monomer to be grafted is volatile and requires elaborate, complicated and often expensive apparatus and techniques to prevent escape of the volatile monomer from the polymer melt. Usually, the volatile monomer is both toxic and flammable, posing risks to personnel and equipment~
32,836-F -1 ~J~
~;~9~3~
6~693-~195 In addition, monomers such as acrylic acid, for example, are too reactive to be conveniently grafted to the polymer.
Generally, such graft monomers will homopolymeri~e to an undesirable extent and not react with the polymer to be ~rafted to the desired extent.
Fu.rther, many monomers are not miscihle or soluble in the polymer melt, resulting in poor disp~rsion of the monomer in the graft polymer product and considerable quantities of the monomer intended to be yrafted being homopolymerized.
Further still, many monomers are :Li~uid at room temperature and are consequently difficult to mix with a normally solid polymer substrate and too volatile to mix with a molten polymer substrate.
The present invention avoids the foregoing problems associated with the prior art by employing a Diels Alder adduct of the monomer desired to be grafted which decomposes into the monomer to be graEted and conjugated diene at the grafting conditions.
The present invention provides a retro Diels Alder-assisted gr~fting method, comprising the steps of:
(a) mixing polyolefin or vinyl, polymer substrate and DielsAlder adduct, said Diels Alder adduct not substantially decomposing below about 120C. and substantially decomposing at a temperature of ~rom about 120C. to about 300C. into conjugated diene and ethylenically unsaturated monomer of the ~ormula RlR2C'=CHR3 wherein Rl is hydrogen, methyl or ethyl; R2 is hydrogen, methyl, ethyl or vinyl; and R3 is hydroxyl, cyano, ~z~
formyl, acetyl, propanoyl, phenyl, ~rialkoxysilyl, hydroxyphenyl~
isocyanato, pyridinyl or amino ~hen R2 is vinyl r and R3 is hydroxyl, cyano, formyl, acetyl, propanoyl, phenyl, trialkoxysilyl, hydroxy-phenyl, isocyanate, pyridinyl or amlno when R2 is hydrogen, methyl or ethyl;
(b~ heating said mixture to a temperature of from about 120C. to about 300C. sufficient to substantially decompose said Diels Alder adduct into said conjugated diene and said ethylenically unsa~urated monomer; and (c) inducing graft polymerization of ~aid ethylenically unsaturated monomer onto said polymer substrate, thereby forming a graft copolymer.
The present invention provides a process of grafting ethylenically uns~t.urated monomer onto a polyolefin or a vinyl polymer. The process includes the step of mixing a polyolefin or vinyl polymer substrate with a Diels Alder adduct of the ethylenically unsaturated monomer to be grafted. The Diels Alder adduct is stable below 120 C and substantially decomposes into conjugated diene and the ethylenically unsaturated monomer ~o be ~0 grafted at a temperature of from 1~0 to 300C.
The method also includes the step of heatin~ the polymer substrate/Diels Alder adduct mixture to a -2a-~9~Z
temperature o~ from 120 to 300C sufficient to substantially decompose the Diels Alder adduct into the conjugated diene and the ethylenically unsaturated monomer to be grafted.
The method ~urther includes the step of inducing gra~t polymerization of the ethylenically unsaturated monomer onto the polyolefin or vinyl polymer substrate, thereby forming a graft polymer.
Optionally, the method may also include the step of devolatilizing the gra~t copolymer to remove unreacted Diels Alder adduct, conjugated diene and ethylenically unsaturated monomer therefrom.
In the practice of the present invention , a polymer substrate is mixed and heated with a Diels Alder adduct which decomposes upon heating into conjugated diene and ethylenically unsaturated monomer.
The ethylenically unsaturated monomer produced by the decomposition o~ the Diels Alder adduct is then grafted onto the polymer substrate. If desired, any unreacted Diels Alder adduct and decomposition products thereof may be removed by devolatilizing the gra~t polymer.
The polymers contemplated as suitable substrates in the present method include polyolefins and vinyl polymers. Polyolefins include, ~or example, homopolymers and copolymers of one or more olefins such 3 as ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-pentene, 1-hexene and 1-octene. Fur-ther, the polyolefins also include olefins copolymerized with relativey minor amounts of monomers copolymerizable therewith, such as, for example: vinyl aryls such as styrene, substituted styrenes, vinyl naphthalene, vinyl ~ 2 ~ d and vinylidene halides such as vinyl chloride and vinylidene bromide; vinyl esters such as vinyl acetate, vinyl propionate and vinyl chloroacetate; acrylic and ~-alkyl acrylic acids, and the alkyl esters, amides and nitriles thereof, such as acrylic acid, chloroacrylic acid, methacryliac acid, methyl acrylate, acrylamide, N-methyl acrylamide, acrylonitrile9 choroacrylonitrile and methacrylonitrile; alkyl esters of maleic and fumaric acid such as dimethyl maleate and diethyl fumarate; vinyl alkyl ethers and ketones such as vinyl methyl ether, vinyl ethyl ether, 2-chloroethyl vinyl ether, methyl vinyl ketone and ethyl vinyl ketone; and other copolymerizable monomers such as carbon mono~ide Preferred polyolefins include low density polyethylene, high density polyethylene, linear low density polyethylene, ethylene-propylene rubbers and plYPrOpylene Suitable vinyl polymers include, for example, homopolymers and copolymers of one or more vinyl compound such as: vinyl aryls such as styrene, substituted styrenes and vinyl napthalene; vinyl and vinyldene halidss such as vinyl chlorlde, vinylidene chloride and vinylidene bromide; vinyl esters such as vinyl acetate, vinyl propionate and vinyl chloroacetate; acrylic and ~-alkyl acrylic acids, and the alkyl esters, amides and nitriles thereof, such as acrylic acid, chloroacrylic acid, methacrylic acid, methyl acrylate, acrylamide, N-methyl acrylamide, acrylonitrile, chloroacrylonitrile and methacrylonitile; and vinyl alkyl ethers and ketones such as vinyl methyl ether, vinyl ethyl ether, 2-chloroethyl ether, methyl vinyl ketone and ethyl vinyl 32,836-F -~-~ ~ ~ 9 3 ketone. Further, the vinyl polymers also include vinyl compounds copolymerized with relatively minor amount of monomers copolymerizable therewith such as, for example: olefins such as ethylene, propylene and 1-butene; alkyl esters of maleic and fumaric acid such asdimethyl maleate and diethyl fumarate; and other copolymerizable monomers such as carbon monoxide.
Preferred vlnyl polymer3 include polystyrene and block copolymers of styrene and butadiene.
The Diels Alder adducts contemplated as suitable in the method include those which decompose upon heating into conjugated diene and ethylenically unsaturated monomer. The Diels Alder adduct must not substantially decompose below 120C in order to permit adequate mixing of the Diels Alder adduct with the polymer substrate before grafting, and must substantially decompose below 300C to avoid degradation of the substrate polymer. As used herein with respect to the Viels Alder adduct 9 the phrase "not substantially decomposed" means that not more than about lO percent decomposed into the diene and carbonyl monomer constituents, and the phrase "substantially decomposed" means that at least 90 percent of the adduct is so decomposed.
The Diels Alder adduct is preferably also substantially nonvolative below 120C to further facilitate blending of the adduct with the polymer substrate. As used herein, the term "nonvolatile"
means having a vapor pressure of about 0O5 atm or less at the specified temperature.
32,836-F ~5-3~
The thermal decomposition products of the Diels Alder adduct include conjugated diene and ethylenically unsaturated monomer. Contemplated suitable diene decomposition constituents include, for example:
acyclic diens such as 1,3-butad ene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene and 1,3,5-hexatriene; cyclic dienes such as l,3-cyclopentadiene, 1,3-cyclohexadiene, 1-methyl-1,3-cyclohexadiene, and 5-methyl-1,3-cyclohexadiene; and heterocyclic dienes such as furan and thiophene.
Contemplated ethylenically unsaturated monomers produced from thermal decomposition of the Diels ~lder adduct generally conform to the formula RlR2C-CHR3 wherein Rl is hydrogen, methyl or ethyl, R2 is hydrogen, methyl, ethyl or vinyl, and R3 is hydroxyl, carboxyl, cyano, ~ormyl, acetyl, propanoyl, phenyl9 trialkoxysilyl, hydroxyphenyl, isocyanato, pyridinyl or amino.
Specific representative examples of ethylenically unsaturated monomers produced from the thermal decomposition of the Diels Alder adduct include: conjugated ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, chloroacrylic acid, crotonic acid, angelic acid, senecoic acid, ~-vinylacrylic acid, fumaric acid9 itaconic acid and glutaconic acid;
conju~ated ethylenically unsaturated carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride and glutaconic anhydride; and alkyl vinyl ketones such as methyl vinyl ketone and ethyl vinyl ketone.
The Diels Alder adduct may generally be prepared by reacting the conjugated diene and the 32,836-F -6-~2.9~3g;~
ethylenically unsaturated monomer under reaction conditions effective to form the adduct.
Specific representative examples of suitable Diels Alder adducts and their respective conjegated diene and ethylenically unsaturated monomer thermal decomposition products are listed in Table I.
Decom~osition Products Adduct Diene Monomer 5-norbornene-2- cyclopentadiene ~-vinylacr~lic acid ac~ylic acid 15 l-~ethoxybicyclo- 1-methi~y-1,3- vinyl methyl ket~ne [2.2.2~ oct-5-en-2- cyclohexadiene dimer yl methyl ketone 5-norbornene-2- 1,3-cy~lopentadiene ac~ylic acid carboxylic acid dimer The mix.~.ng of the polymer substrate and the Diels Alder adduct may be accomplished in either solid or molten form as by, for example, dry blending, Banbury mixing, in a roll mill or in a mixing extruder.
Masterbatches which contain a relatively high percentage of the Diels Alder adduct in a polymer substrate may also be employed by mixing the materbatch with the polymer substrate to obtain the desired proportion of Diels Alder adductO Preferably, the 3 mixing is done at a temperature below which the Diels Alder adduct is volatile and below which the Diels Alder adduct is not substantially decomposed.
The mixture is then heated to a temperature at which the Diels Alder adduct substantially decomposes into the diane and monomer constituents, but not above 32,836-F -7-300C in order to avoid degradation of the polymer substrate. Preferably, the temperature to which the mixture is heated is from 150 to 250C.
Graft polymerization of the monomer onto the polymer substrate in the molten mixture is then induced by the heating alone, but is preferably induced by the heating in the presence of a free-radical eatalyst such as air, peroxides or actinic light, and more preferably also under high shear conditions.
The mixing, heating and inducing graft polymerization is preferably done simultaneously, either on a batch or continuous basis~ In a preferred embodiment, the process is ef~ected with a screw~type extruder.
Generally, from 0.2 to 5 parts by weight of the D els Alder adduct are mixed with 100 parts by ~leight of the polymer substrate, preferably from 1 to 3 parts by weight of the adduct per 100 parts polymer substrate.
ExamDle 1 Using a Haake Buchler Rheocord System 40 mixing device, 40 g of an ethylene-octene LLDPE having a density of about 0.920 g/cc and a mel~ index o~ 6.6 were fluxed in the mixing head at 50 rpm at a temperature of 220C. Over a period of 1 minute, 8.2 mg-moles of 5-norborene-2-carboxylic acid and 30 ~l (2.~ mg) of 2,5-dimethyl-2,5-di~t-butyl peroxy)hex-3-yne were added to the fluxing LLDPE with a syringe through an injection ram modified for this purpose.
The mixer speed was then increased to 200 rpm ~or 6 32,836-F ~8-3~J2 g minutes. The graft copolymer product was then removed from the mixer and cooled.
The graft copolymer product was dissolved in xylene at 10C, precipitated with acetone~ filtered, and dried in a vacuum oven at 60C ~or 14 hours to remove residual low molecular weight materials. By titration in 3:1 xylene/butanol with tetra-n-butyl ammonium hydroxide (1.OM in methanol) using thymol blue as an indicator, the graft copolymer product had an acrylic acid content of 0.27 weight percent.
The above procedure was repeated except that 8.2 mg-moles of acylic acid were used instead of 5-norborene-2-carboxylic acid. The resulting g graft copolymer had an acrylic acid content of 0.24 weight percent. This example demonstrates that equivalent grafting of a conjugated ethylenically unsaturated carbonyl such as acrylic acid may be achieYed by using a Diels Alder adduct thereo~.
ExamDle 2 Using a Brabender mixer capable of mixing aliquots of up to 50 g of polymer, 40 g of HDPE (0.962 g/cc, melt index 10) were added to the mixing head and allowed to melt for about 30 seconds at 175C at 200 rpm. Over a period of 30 seconds, 21.7 mg-moles of 5-norbornene-2-carboxylic acid were injected into the 3 mixing chamber~ After allowing 15 seconds for mi~ing, 50 ~l of a 50 weight percent solution of dicumyl peroxide In methyl ethyl ketone were injected. After mixing an additional 3 minutes, the grafted copolymer was removed from the chamber and allowed to cool.
The graft copolymer product was dissolved in xylene at 100C, precipitated with aeetone, filtered and $~ h~PrR~
32,836-F -9-z - l o -dried in a vacuum oven 70C for 14 hours to remove residual low molecular weight materials. By infrared spectroscopy, the incorporated acylic acid content was determined to be about 0.14 percent by weight. The graft copolymer had a melt index of ~.08.
The above procedure was repeated except that 21.7 mg-moles of acrylic acid were used instead of the 5-norbornene-2-carboxyic acid. The resulting graft copolymer had an acrylic acid content determined by infrared spectroscopy of about 0.27 weight percent.
However, the melt index of this material was 0.88, indicating that substantially more crosslinkage occurred when acrylic acid was used instead of the Diels Alder adduct thereof.
ExamDle 3 The procedure of Example 2 was repeated with 24.9 mg-moles of 1-methoxybicyclo[2.2.2]oct-5-ene-2-yl methyl ketone irlstead of 5-norbornene-2-carboxylic acid, and 100 ~l of 2,5-dimethyl-2,5-di~t-butyl-peroxy)hex-3-yne were added in place of the 50 weight percent dicumyl peroxide in methyl ethyl ketone. By IR
spectroscopy,-the resulting graft copolymer contained about 0.15 percent vinyl methyl ketone by weight.
Exam~le ~
To demonstrate that various Dlels Alder adducts are suitably employed in the present method, the IR
absorption of various Diels Alder adducts were determined and compared with the saturated Diels Qlder adduct and with graft HDPE copolymers thereof. The monomers were grafted to high density polyethylene (0.954 gcc, 5 melt index) in a Haake Buchler System ~0 32~36-F -10-3~
mixing device by introducing 38 g of the HDPE into the mixing head at 300C.
Following a one minute melt time, 2Q4 mg~moles of the Diels Alder adduct (or maleic anhydride monomer) to be examined were added to the mixing head and mixed with the HDPE for 15 minutes at 250 rpm rotor speed.
The graft copolymer was then removed from the chamber9 cooled, dissolved in hot 1,2,4-trichlorobenzene at 2 weight percent, precipitated with an equal volume of 2-butanone, filtered and dried in a vacuum oven to substantially remove residual monomer. The graft copolymers were then analyzed by infrared spectroscopy to determine the peak carbonyl absorption wavelengths.
The data is presented in Table II along with the peak carbonyl absorption values for the adduct and the saturated adduct.
32,836-F
~2~3~2 Table II
LLDPE
Unsaturated Saturated Graft Copolymer Monomer Adduct/ Absorption absorption Absorptions 5No. Monomer ~ (cml) tcm 1) 1 Maleic 1788, 1863 1792, 1863 1797, 1873.5 anhydride 2 Tetrahydro- 1780, 1847 1798, 1866 --phthalic anhydride 10 3 ~icyclo[2.2.1~ 1775, 1856 1788, 1865 1795,187 hept-5-ene-2,3-diGar-boxylic anhydride 4 7-Oxabicyclo 1795, 1865 1795, 1864 1795.5, 1874 12.2.1]hept-5-ene-2,3-dicarboxylic anhydride 6-Methyl- 1785, 1863 NA 1796,1873 bicyclo [2.2.1]-hept-5-ene-2,3-2~ dicarboxylic v anhydride 6 Bicyclo[2.2.2] 1788, 1865 NA 1798, 1874 oct-5-ene-2,3-dicar-boxylic anhydride 25 7 6-Methyl- 1773, 1840 NA 1797, 1874 tetrahydropht halic anhydride 8 ~icyclo[2.2.2~ 1780, 1860 NA ~778-1788, 1857 oct-7-ene-2,3,5,6-tetra-carboxylic acid dianhydride Note for Table II:
NA = saturated absorptions not determined 32~v36-F -12-~3l2~3~2 By comparing the IR absorption of various graft copolymers of Diels Alder adducts, it is seen either that the decomposition products (maleic anhydride) were grafted (as with monomers 3 to 7), the Diels Alder adduct itself was grafted (as with monomer 8), or ~he adduct did not result in any grafting at all (as with monomer 2), depending on the decomposition temperature of the adduct. It is believed that monomer No. 8 did not yield any maleic anhydride grafting because of its relatively hi~h decomposition temperature, whereas monomer No. 2 did not graft at all because of its relative volatility.
ExamDle 5 A series of tests were run to demonstrate a technique for screening the suitability of proposed Diels Alder adducts for use in the present method. A
38.1 cm OV-17 gas chromatograph column was used in a 20~ Finnigan 3200~GC-MS at 100G. A Pyroprobe~pyrolysis chamber was connected to the unit as the injection point. Samples of the Diels Alder adduct to be tested were placed in quartz tubes and pyrolysis was incurred for a period of 10 seconds at a predetermined temperature. Helium flowing through the Pyroprobe chamber carried the decomposition products onto the gas chromatrograph column and then to the mass spectrometer for identification. The results are presented in Table III.
~P~ R
32,836-F 13-3~:2 TABLE III
Diels Alder Adduct Result of Pvrolvsis 5-norbornene-2~acrylic acid Decomposed into ~-vinyl acrylic acid and cyclopentadiene at 200C
l-methoxybicyclo[2.2.2~oct- Decomposed into vinyl methyl 5-ene-2-yl-methyl ketone ketone and the dimer of 1-methoxycyclohex-1,3-diene at 5-norborene-2-carboxylic acid Decomposed into acrylic acid and the dimer of cyclopentadiene at 200C
5-norbornene-2-carbonitrile Stable to 300C
15 5-norbornene-2-carboxaldehyde Stable to 300C
5-norbornene-2-ol Stable to 300C
cyclohex-4-ene-1,2-dicarboxylic Stable to 450C
anhydride l-methoxybicyclo[2.2.2~oct- Stable between 100 and 20 s-ene-2-carbonitrile 300C
3o 32,836-F -14-
POLYMER GRAFTING PROCESS
This invention relates to a method o~ grafting an ethylenically unsaturated monomer onto a polyolefin or polyvinyl polymer substrate and particularly to such a method in which a Diels Alder adduct of the monomer to be grafted is employed to provide the source of the ethylenically unsaturated monomer through a retro Diels Alder mechanism.
The grafting of ethylenically unsaturated monomers onto a molten polymer substrate with or without a free radical initiator is well known. For example 9 methods of grafting monomers such as maleic anhydride onto polyethylene in an extruder are described in U. S. Patents 3,882,194 and 3,873,643.
In many applications~ however~ the monomer to be grafted is volatile and requires elaborate, complicated and often expensive apparatus and techniques to prevent escape of the volatile monomer from the polymer melt. Usually, the volatile monomer is both toxic and flammable, posing risks to personnel and equipment~
32,836-F -1 ~J~
~;~9~3~
6~693-~195 In addition, monomers such as acrylic acid, for example, are too reactive to be conveniently grafted to the polymer.
Generally, such graft monomers will homopolymeri~e to an undesirable extent and not react with the polymer to be ~rafted to the desired extent.
Fu.rther, many monomers are not miscihle or soluble in the polymer melt, resulting in poor disp~rsion of the monomer in the graft polymer product and considerable quantities of the monomer intended to be yrafted being homopolymerized.
Further still, many monomers are :Li~uid at room temperature and are consequently difficult to mix with a normally solid polymer substrate and too volatile to mix with a molten polymer substrate.
The present invention avoids the foregoing problems associated with the prior art by employing a Diels Alder adduct of the monomer desired to be grafted which decomposes into the monomer to be graEted and conjugated diene at the grafting conditions.
The present invention provides a retro Diels Alder-assisted gr~fting method, comprising the steps of:
(a) mixing polyolefin or vinyl, polymer substrate and DielsAlder adduct, said Diels Alder adduct not substantially decomposing below about 120C. and substantially decomposing at a temperature of ~rom about 120C. to about 300C. into conjugated diene and ethylenically unsaturated monomer of the ~ormula RlR2C'=CHR3 wherein Rl is hydrogen, methyl or ethyl; R2 is hydrogen, methyl, ethyl or vinyl; and R3 is hydroxyl, cyano, ~z~
formyl, acetyl, propanoyl, phenyl, ~rialkoxysilyl, hydroxyphenyl~
isocyanato, pyridinyl or amino ~hen R2 is vinyl r and R3 is hydroxyl, cyano, formyl, acetyl, propanoyl, phenyl, trialkoxysilyl, hydroxy-phenyl, isocyanate, pyridinyl or amlno when R2 is hydrogen, methyl or ethyl;
(b~ heating said mixture to a temperature of from about 120C. to about 300C. sufficient to substantially decompose said Diels Alder adduct into said conjugated diene and said ethylenically unsa~urated monomer; and (c) inducing graft polymerization of ~aid ethylenically unsaturated monomer onto said polymer substrate, thereby forming a graft copolymer.
The present invention provides a process of grafting ethylenically uns~t.urated monomer onto a polyolefin or a vinyl polymer. The process includes the step of mixing a polyolefin or vinyl polymer substrate with a Diels Alder adduct of the ethylenically unsaturated monomer to be grafted. The Diels Alder adduct is stable below 120 C and substantially decomposes into conjugated diene and the ethylenically unsaturated monomer ~o be ~0 grafted at a temperature of from 1~0 to 300C.
The method also includes the step of heatin~ the polymer substrate/Diels Alder adduct mixture to a -2a-~9~Z
temperature o~ from 120 to 300C sufficient to substantially decompose the Diels Alder adduct into the conjugated diene and the ethylenically unsaturated monomer to be grafted.
The method ~urther includes the step of inducing gra~t polymerization of the ethylenically unsaturated monomer onto the polyolefin or vinyl polymer substrate, thereby forming a graft polymer.
Optionally, the method may also include the step of devolatilizing the gra~t copolymer to remove unreacted Diels Alder adduct, conjugated diene and ethylenically unsaturated monomer therefrom.
In the practice of the present invention , a polymer substrate is mixed and heated with a Diels Alder adduct which decomposes upon heating into conjugated diene and ethylenically unsaturated monomer.
The ethylenically unsaturated monomer produced by the decomposition o~ the Diels Alder adduct is then grafted onto the polymer substrate. If desired, any unreacted Diels Alder adduct and decomposition products thereof may be removed by devolatilizing the gra~t polymer.
The polymers contemplated as suitable substrates in the present method include polyolefins and vinyl polymers. Polyolefins include, ~or example, homopolymers and copolymers of one or more olefins such 3 as ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-pentene, 1-hexene and 1-octene. Fur-ther, the polyolefins also include olefins copolymerized with relativey minor amounts of monomers copolymerizable therewith, such as, for example: vinyl aryls such as styrene, substituted styrenes, vinyl naphthalene, vinyl ~ 2 ~ d and vinylidene halides such as vinyl chloride and vinylidene bromide; vinyl esters such as vinyl acetate, vinyl propionate and vinyl chloroacetate; acrylic and ~-alkyl acrylic acids, and the alkyl esters, amides and nitriles thereof, such as acrylic acid, chloroacrylic acid, methacryliac acid, methyl acrylate, acrylamide, N-methyl acrylamide, acrylonitrile9 choroacrylonitrile and methacrylonitrile; alkyl esters of maleic and fumaric acid such as dimethyl maleate and diethyl fumarate; vinyl alkyl ethers and ketones such as vinyl methyl ether, vinyl ethyl ether, 2-chloroethyl vinyl ether, methyl vinyl ketone and ethyl vinyl ketone; and other copolymerizable monomers such as carbon mono~ide Preferred polyolefins include low density polyethylene, high density polyethylene, linear low density polyethylene, ethylene-propylene rubbers and plYPrOpylene Suitable vinyl polymers include, for example, homopolymers and copolymers of one or more vinyl compound such as: vinyl aryls such as styrene, substituted styrenes and vinyl napthalene; vinyl and vinyldene halidss such as vinyl chlorlde, vinylidene chloride and vinylidene bromide; vinyl esters such as vinyl acetate, vinyl propionate and vinyl chloroacetate; acrylic and ~-alkyl acrylic acids, and the alkyl esters, amides and nitriles thereof, such as acrylic acid, chloroacrylic acid, methacrylic acid, methyl acrylate, acrylamide, N-methyl acrylamide, acrylonitrile, chloroacrylonitrile and methacrylonitile; and vinyl alkyl ethers and ketones such as vinyl methyl ether, vinyl ethyl ether, 2-chloroethyl ether, methyl vinyl ketone and ethyl vinyl 32,836-F -~-~ ~ ~ 9 3 ketone. Further, the vinyl polymers also include vinyl compounds copolymerized with relatively minor amount of monomers copolymerizable therewith such as, for example: olefins such as ethylene, propylene and 1-butene; alkyl esters of maleic and fumaric acid such asdimethyl maleate and diethyl fumarate; and other copolymerizable monomers such as carbon monoxide.
Preferred vlnyl polymer3 include polystyrene and block copolymers of styrene and butadiene.
The Diels Alder adducts contemplated as suitable in the method include those which decompose upon heating into conjugated diene and ethylenically unsaturated monomer. The Diels Alder adduct must not substantially decompose below 120C in order to permit adequate mixing of the Diels Alder adduct with the polymer substrate before grafting, and must substantially decompose below 300C to avoid degradation of the substrate polymer. As used herein with respect to the Viels Alder adduct 9 the phrase "not substantially decomposed" means that not more than about lO percent decomposed into the diene and carbonyl monomer constituents, and the phrase "substantially decomposed" means that at least 90 percent of the adduct is so decomposed.
The Diels Alder adduct is preferably also substantially nonvolative below 120C to further facilitate blending of the adduct with the polymer substrate. As used herein, the term "nonvolatile"
means having a vapor pressure of about 0O5 atm or less at the specified temperature.
32,836-F ~5-3~
The thermal decomposition products of the Diels Alder adduct include conjugated diene and ethylenically unsaturated monomer. Contemplated suitable diene decomposition constituents include, for example:
acyclic diens such as 1,3-butad ene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene and 1,3,5-hexatriene; cyclic dienes such as l,3-cyclopentadiene, 1,3-cyclohexadiene, 1-methyl-1,3-cyclohexadiene, and 5-methyl-1,3-cyclohexadiene; and heterocyclic dienes such as furan and thiophene.
Contemplated ethylenically unsaturated monomers produced from thermal decomposition of the Diels ~lder adduct generally conform to the formula RlR2C-CHR3 wherein Rl is hydrogen, methyl or ethyl, R2 is hydrogen, methyl, ethyl or vinyl, and R3 is hydroxyl, carboxyl, cyano, ~ormyl, acetyl, propanoyl, phenyl9 trialkoxysilyl, hydroxyphenyl, isocyanato, pyridinyl or amino.
Specific representative examples of ethylenically unsaturated monomers produced from the thermal decomposition of the Diels Alder adduct include: conjugated ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, chloroacrylic acid, crotonic acid, angelic acid, senecoic acid, ~-vinylacrylic acid, fumaric acid9 itaconic acid and glutaconic acid;
conju~ated ethylenically unsaturated carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride and glutaconic anhydride; and alkyl vinyl ketones such as methyl vinyl ketone and ethyl vinyl ketone.
The Diels Alder adduct may generally be prepared by reacting the conjugated diene and the 32,836-F -6-~2.9~3g;~
ethylenically unsaturated monomer under reaction conditions effective to form the adduct.
Specific representative examples of suitable Diels Alder adducts and their respective conjegated diene and ethylenically unsaturated monomer thermal decomposition products are listed in Table I.
Decom~osition Products Adduct Diene Monomer 5-norbornene-2- cyclopentadiene ~-vinylacr~lic acid ac~ylic acid 15 l-~ethoxybicyclo- 1-methi~y-1,3- vinyl methyl ket~ne [2.2.2~ oct-5-en-2- cyclohexadiene dimer yl methyl ketone 5-norbornene-2- 1,3-cy~lopentadiene ac~ylic acid carboxylic acid dimer The mix.~.ng of the polymer substrate and the Diels Alder adduct may be accomplished in either solid or molten form as by, for example, dry blending, Banbury mixing, in a roll mill or in a mixing extruder.
Masterbatches which contain a relatively high percentage of the Diels Alder adduct in a polymer substrate may also be employed by mixing the materbatch with the polymer substrate to obtain the desired proportion of Diels Alder adductO Preferably, the 3 mixing is done at a temperature below which the Diels Alder adduct is volatile and below which the Diels Alder adduct is not substantially decomposed.
The mixture is then heated to a temperature at which the Diels Alder adduct substantially decomposes into the diane and monomer constituents, but not above 32,836-F -7-300C in order to avoid degradation of the polymer substrate. Preferably, the temperature to which the mixture is heated is from 150 to 250C.
Graft polymerization of the monomer onto the polymer substrate in the molten mixture is then induced by the heating alone, but is preferably induced by the heating in the presence of a free-radical eatalyst such as air, peroxides or actinic light, and more preferably also under high shear conditions.
The mixing, heating and inducing graft polymerization is preferably done simultaneously, either on a batch or continuous basis~ In a preferred embodiment, the process is ef~ected with a screw~type extruder.
Generally, from 0.2 to 5 parts by weight of the D els Alder adduct are mixed with 100 parts by ~leight of the polymer substrate, preferably from 1 to 3 parts by weight of the adduct per 100 parts polymer substrate.
ExamDle 1 Using a Haake Buchler Rheocord System 40 mixing device, 40 g of an ethylene-octene LLDPE having a density of about 0.920 g/cc and a mel~ index o~ 6.6 were fluxed in the mixing head at 50 rpm at a temperature of 220C. Over a period of 1 minute, 8.2 mg-moles of 5-norborene-2-carboxylic acid and 30 ~l (2.~ mg) of 2,5-dimethyl-2,5-di~t-butyl peroxy)hex-3-yne were added to the fluxing LLDPE with a syringe through an injection ram modified for this purpose.
The mixer speed was then increased to 200 rpm ~or 6 32,836-F ~8-3~J2 g minutes. The graft copolymer product was then removed from the mixer and cooled.
The graft copolymer product was dissolved in xylene at 10C, precipitated with acetone~ filtered, and dried in a vacuum oven at 60C ~or 14 hours to remove residual low molecular weight materials. By titration in 3:1 xylene/butanol with tetra-n-butyl ammonium hydroxide (1.OM in methanol) using thymol blue as an indicator, the graft copolymer product had an acrylic acid content of 0.27 weight percent.
The above procedure was repeated except that 8.2 mg-moles of acylic acid were used instead of 5-norborene-2-carboxylic acid. The resulting g graft copolymer had an acrylic acid content of 0.24 weight percent. This example demonstrates that equivalent grafting of a conjugated ethylenically unsaturated carbonyl such as acrylic acid may be achieYed by using a Diels Alder adduct thereo~.
ExamDle 2 Using a Brabender mixer capable of mixing aliquots of up to 50 g of polymer, 40 g of HDPE (0.962 g/cc, melt index 10) were added to the mixing head and allowed to melt for about 30 seconds at 175C at 200 rpm. Over a period of 30 seconds, 21.7 mg-moles of 5-norbornene-2-carboxylic acid were injected into the 3 mixing chamber~ After allowing 15 seconds for mi~ing, 50 ~l of a 50 weight percent solution of dicumyl peroxide In methyl ethyl ketone were injected. After mixing an additional 3 minutes, the grafted copolymer was removed from the chamber and allowed to cool.
The graft copolymer product was dissolved in xylene at 100C, precipitated with aeetone, filtered and $~ h~PrR~
32,836-F -9-z - l o -dried in a vacuum oven 70C for 14 hours to remove residual low molecular weight materials. By infrared spectroscopy, the incorporated acylic acid content was determined to be about 0.14 percent by weight. The graft copolymer had a melt index of ~.08.
The above procedure was repeated except that 21.7 mg-moles of acrylic acid were used instead of the 5-norbornene-2-carboxyic acid. The resulting graft copolymer had an acrylic acid content determined by infrared spectroscopy of about 0.27 weight percent.
However, the melt index of this material was 0.88, indicating that substantially more crosslinkage occurred when acrylic acid was used instead of the Diels Alder adduct thereof.
ExamDle 3 The procedure of Example 2 was repeated with 24.9 mg-moles of 1-methoxybicyclo[2.2.2]oct-5-ene-2-yl methyl ketone irlstead of 5-norbornene-2-carboxylic acid, and 100 ~l of 2,5-dimethyl-2,5-di~t-butyl-peroxy)hex-3-yne were added in place of the 50 weight percent dicumyl peroxide in methyl ethyl ketone. By IR
spectroscopy,-the resulting graft copolymer contained about 0.15 percent vinyl methyl ketone by weight.
Exam~le ~
To demonstrate that various Dlels Alder adducts are suitably employed in the present method, the IR
absorption of various Diels Alder adducts were determined and compared with the saturated Diels Qlder adduct and with graft HDPE copolymers thereof. The monomers were grafted to high density polyethylene (0.954 gcc, 5 melt index) in a Haake Buchler System ~0 32~36-F -10-3~
mixing device by introducing 38 g of the HDPE into the mixing head at 300C.
Following a one minute melt time, 2Q4 mg~moles of the Diels Alder adduct (or maleic anhydride monomer) to be examined were added to the mixing head and mixed with the HDPE for 15 minutes at 250 rpm rotor speed.
The graft copolymer was then removed from the chamber9 cooled, dissolved in hot 1,2,4-trichlorobenzene at 2 weight percent, precipitated with an equal volume of 2-butanone, filtered and dried in a vacuum oven to substantially remove residual monomer. The graft copolymers were then analyzed by infrared spectroscopy to determine the peak carbonyl absorption wavelengths.
The data is presented in Table II along with the peak carbonyl absorption values for the adduct and the saturated adduct.
32,836-F
~2~3~2 Table II
LLDPE
Unsaturated Saturated Graft Copolymer Monomer Adduct/ Absorption absorption Absorptions 5No. Monomer ~ (cml) tcm 1) 1 Maleic 1788, 1863 1792, 1863 1797, 1873.5 anhydride 2 Tetrahydro- 1780, 1847 1798, 1866 --phthalic anhydride 10 3 ~icyclo[2.2.1~ 1775, 1856 1788, 1865 1795,187 hept-5-ene-2,3-diGar-boxylic anhydride 4 7-Oxabicyclo 1795, 1865 1795, 1864 1795.5, 1874 12.2.1]hept-5-ene-2,3-dicarboxylic anhydride 6-Methyl- 1785, 1863 NA 1796,1873 bicyclo [2.2.1]-hept-5-ene-2,3-2~ dicarboxylic v anhydride 6 Bicyclo[2.2.2] 1788, 1865 NA 1798, 1874 oct-5-ene-2,3-dicar-boxylic anhydride 25 7 6-Methyl- 1773, 1840 NA 1797, 1874 tetrahydropht halic anhydride 8 ~icyclo[2.2.2~ 1780, 1860 NA ~778-1788, 1857 oct-7-ene-2,3,5,6-tetra-carboxylic acid dianhydride Note for Table II:
NA = saturated absorptions not determined 32~v36-F -12-~3l2~3~2 By comparing the IR absorption of various graft copolymers of Diels Alder adducts, it is seen either that the decomposition products (maleic anhydride) were grafted (as with monomers 3 to 7), the Diels Alder adduct itself was grafted (as with monomer 8), or ~he adduct did not result in any grafting at all (as with monomer 2), depending on the decomposition temperature of the adduct. It is believed that monomer No. 8 did not yield any maleic anhydride grafting because of its relatively hi~h decomposition temperature, whereas monomer No. 2 did not graft at all because of its relative volatility.
ExamDle 5 A series of tests were run to demonstrate a technique for screening the suitability of proposed Diels Alder adducts for use in the present method. A
38.1 cm OV-17 gas chromatograph column was used in a 20~ Finnigan 3200~GC-MS at 100G. A Pyroprobe~pyrolysis chamber was connected to the unit as the injection point. Samples of the Diels Alder adduct to be tested were placed in quartz tubes and pyrolysis was incurred for a period of 10 seconds at a predetermined temperature. Helium flowing through the Pyroprobe chamber carried the decomposition products onto the gas chromatrograph column and then to the mass spectrometer for identification. The results are presented in Table III.
~P~ R
32,836-F 13-3~:2 TABLE III
Diels Alder Adduct Result of Pvrolvsis 5-norbornene-2~acrylic acid Decomposed into ~-vinyl acrylic acid and cyclopentadiene at 200C
l-methoxybicyclo[2.2.2~oct- Decomposed into vinyl methyl 5-ene-2-yl-methyl ketone ketone and the dimer of 1-methoxycyclohex-1,3-diene at 5-norborene-2-carboxylic acid Decomposed into acrylic acid and the dimer of cyclopentadiene at 200C
5-norbornene-2-carbonitrile Stable to 300C
15 5-norbornene-2-carboxaldehyde Stable to 300C
5-norbornene-2-ol Stable to 300C
cyclohex-4-ene-1,2-dicarboxylic Stable to 450C
anhydride l-methoxybicyclo[2.2.2~oct- Stable between 100 and 20 s-ene-2-carbonitrile 300C
3o 32,836-F -14-
Claims (18)
1. A retro Diels Alder-assisted grafting method, comprising the steps of:
(a) mixing polyolefin or vinyl polymer substrate and Diels Alder adduct, said Diels Alder adduct not substantially decomposing below about 1 20°C. and substantially decomposing at a temperature of from about 120°C. to about 300°C. into conjugated diene and ethylenically unsaturated monomer of the formula R1R2C=CHR3 wherein R1 is hydrogen, methyl or ethyl; R2 is hydrogen, methyl, ethyl or vinyl; and R3 is hydroxyl, cyano, formyl, acetyl, propanoyl, phenyl, trialkoxysilyl, hydroxyphenyl, isocyanato, pyridinyl or amino when R2 is vinyl, and R3 is hydroxyl, cyano, formyl, acetyl, propanoyl, phenyl, trialkoxysilyl, hydroxy-phenyi, isocyanate, pyridinyl or amino when R2 is hydrogen, methyl or ethyl;
(b) heating said mixture to a temperature of from about 120°C. to about 300°C. sufficient to substantially decompose said Diels Alder adduct into said conjugated diene anct said ethylenically unsaturated monomer; and 32 ,836-F
(c) inducing graft polymerization of said ethylenically unsaturated monomer onto said polymer substrate, thereby forming a graft copolymer.
(a) mixing polyolefin or vinyl polymer substrate and Diels Alder adduct, said Diels Alder adduct not substantially decomposing below about 1 20°C. and substantially decomposing at a temperature of from about 120°C. to about 300°C. into conjugated diene and ethylenically unsaturated monomer of the formula R1R2C=CHR3 wherein R1 is hydrogen, methyl or ethyl; R2 is hydrogen, methyl, ethyl or vinyl; and R3 is hydroxyl, cyano, formyl, acetyl, propanoyl, phenyl, trialkoxysilyl, hydroxyphenyl, isocyanato, pyridinyl or amino when R2 is vinyl, and R3 is hydroxyl, cyano, formyl, acetyl, propanoyl, phenyl, trialkoxysilyl, hydroxy-phenyi, isocyanate, pyridinyl or amino when R2 is hydrogen, methyl or ethyl;
(b) heating said mixture to a temperature of from about 120°C. to about 300°C. sufficient to substantially decompose said Diels Alder adduct into said conjugated diene anct said ethylenically unsaturated monomer; and 32 ,836-F
(c) inducing graft polymerization of said ethylenically unsaturated monomer onto said polymer substrate, thereby forming a graft copolymer.
2. The method of claim 1, wherein said polymer substrate is selected from the group consisting of high density polyethylene, low density polyethylene, linear low density polyethylene, ethylene-propylene rubber, polypropylene, polystyrene and styrene-butadiene block copolymers.
3. The method of claim 1, wherein said Diels Alder adduct undergoes said substantial decomposition at a temperature of from about 1 50°C. to about 250°C.
4. The method of claim 1, further comprising the step of:
(d) devolatilizing said graft copolymer to substantially remove therefrom unreacted Diels Alder adduct and decomposition products thereof.
(d) devolatilizing said graft copolymer to substantially remove therefrom unreacted Diels Alder adduct and decomposition products thereof.
5. A retro Diels Alder-assisted grafting method, comprising the steps of:
(a) mixing polymer substrate and Diels Alder adduct, said polymer substrate selected form the group consisting of: high density polyethylene, low density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene rubber, polystyrene and styrene-butadiene block copolymer; said Diels Alder adduct not substantially decomposing below about 150°C. and substantially decomposing at a temperature of from about 150°C. to about 250°C. into conjugated diene and ethylenically unsaturated monomer of the formula 32,836-F
R1R2C = CHR3 wherein R1 is hydrogen, methyl or ethyl; R2 is hydrogen, methyl, ethyl or vinyl; and R3 is carboxyl, acetyl, formyl or propanoyl when R2 is vinyl, and R3 is formyl, acetyl or propanyl when R2 is hydrogen, methyl or ethyl;
(b) heating said mixture to a temperature of from about 1 50°C to about 250°C. sufficient to substantially decompose said Diels Alder adduct into said conjugated diene and said ethylenically unsaturated monomer; and (c) inducing graft polymerization of said ethylenically unsaturated monomer onto said polymer substrate, thereby forming a graft copolymer.
(a) mixing polymer substrate and Diels Alder adduct, said polymer substrate selected form the group consisting of: high density polyethylene, low density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene rubber, polystyrene and styrene-butadiene block copolymer; said Diels Alder adduct not substantially decomposing below about 150°C. and substantially decomposing at a temperature of from about 150°C. to about 250°C. into conjugated diene and ethylenically unsaturated monomer of the formula 32,836-F
R1R2C = CHR3 wherein R1 is hydrogen, methyl or ethyl; R2 is hydrogen, methyl, ethyl or vinyl; and R3 is carboxyl, acetyl, formyl or propanoyl when R2 is vinyl, and R3 is formyl, acetyl or propanyl when R2 is hydrogen, methyl or ethyl;
(b) heating said mixture to a temperature of from about 1 50°C to about 250°C. sufficient to substantially decompose said Diels Alder adduct into said conjugated diene and said ethylenically unsaturated monomer; and (c) inducing graft polymerization of said ethylenically unsaturated monomer onto said polymer substrate, thereby forming a graft copolymer.
6. The method of claim 5, wherein said ethylenically unsaturated monomer is B-vinylacrylic acid.
7. The method of claim 6, wherein said Diels Alder adduct is 5-norbornene-2-acrylic acid.
8. The method of claim 5, wherein said ethylenically unsaturated monomer is vinyl methyl ketone.
9. The method of claim 8, wherein said Diels Alder adduct is 1-methoxybicyclo [2.2.2]oct-5-ene-2-yl methyl ketone.
32,836-F -17-
32,836-F -17-
10. A retro Diels Alder-assisted grafting method, comprising the simulataneous steps of:
(a) mixing at a high shear rate in the presence of free radical catalyst:
(i) polymer substrate selected from the group consisting of:
high density polyethylene, low density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene rubber, polystyrene and styrene-butadiene block copolymer;
and (ii) from about 0.1 to about 10 parts by weight, per 100 parts by weight of said polymer substrate of Diels Alder adduct selected from the group consisting of: 5-norbornene-2-acrylic acid and 1-methoxybicyclo [2.2.2]oct-5-ene-2 yl methyl ketone;
(b) heating said mixture to a temperature of from about 1 50°C. to about 250°C. sufficient to substantially decompose said Diels Alder adduct into conjugated and ethylenically unsaturated monomerselected from the group consisting of: B-vinyl acrylic acid and vinyl methyl ketone; and (c) inducing graft polymerization of said monomer onto said polyrner substrate, thereby forming a graft copolymer.
(a) mixing at a high shear rate in the presence of free radical catalyst:
(i) polymer substrate selected from the group consisting of:
high density polyethylene, low density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene rubber, polystyrene and styrene-butadiene block copolymer;
and (ii) from about 0.1 to about 10 parts by weight, per 100 parts by weight of said polymer substrate of Diels Alder adduct selected from the group consisting of: 5-norbornene-2-acrylic acid and 1-methoxybicyclo [2.2.2]oct-5-ene-2 yl methyl ketone;
(b) heating said mixture to a temperature of from about 1 50°C. to about 250°C. sufficient to substantially decompose said Diels Alder adduct into conjugated and ethylenically unsaturated monomerselected from the group consisting of: B-vinyl acrylic acid and vinyl methyl ketone; and (c) inducing graft polymerization of said monomer onto said polyrner substrate, thereby forming a graft copolymer.
11. The method of claim 10, wherein said Diels Alder adduct is 5-norbornene-2-acrylic acid.
12. The method of claim 10, wherein said Diels Alder adduct is 1-methoxybicycio[2.2.2]oct-5-ene-2-yl methyl ketone.
32,836-F - 18-
32,836-F - 18-
13. The method of claim 10, further comprising the step of devolatilizing said graft copolymer to remove therefrom unreacted Diels Alder adduct and decomposition products thereof.
14. The method of claim 13, wherein said steps are effected on a batch basis.
15. The method of claim 13, wherein said steps are effected on a continuous basis.
16. The method of claim 10, wherein said steps are effected with a screw-type extruder.
17. The method of claim 10, wherein from about 0.2 to about 5 parts by weight of said Diels Alder adduct are mixed with 100 parts by weight of said polymer substrate.
18. The method of claim 10, wherein from about 1 to about 3 parts by weight of said Diels Alder adduct are mixed with 100 parts by weight of said polymer substrate.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/871,741 US4739017A (en) | 1986-06-06 | 1986-06-06 | Retro Diels Alder assisted polymer grafting process |
| CA000558349A CA1299302C (en) | 1986-06-06 | 1988-02-08 | Retro diels alder assisted polymers grafting process |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/871,741 US4739017A (en) | 1986-06-06 | 1986-06-06 | Retro Diels Alder assisted polymer grafting process |
| CA000558349A CA1299302C (en) | 1986-06-06 | 1988-02-08 | Retro diels alder assisted polymers grafting process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1299302C true CA1299302C (en) | 1992-04-21 |
Family
ID=25671703
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000558349A Expired - Lifetime CA1299302C (en) | 1986-06-06 | 1988-02-08 | Retro diels alder assisted polymers grafting process |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1299302C (en) |
-
1988
- 1988-02-08 CA CA000558349A patent/CA1299302C/en not_active Expired - Lifetime
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