CA1183991A - Olefin polymer modified with a substituted maleamic acid - Google Patents
Olefin polymer modified with a substituted maleamic acidInfo
- Publication number
- CA1183991A CA1183991A CA000372597A CA372597A CA1183991A CA 1183991 A CA1183991 A CA 1183991A CA 000372597 A CA000372597 A CA 000372597A CA 372597 A CA372597 A CA 372597A CA 1183991 A CA1183991 A CA 1183991A
- Authority
- CA
- Canada
- Prior art keywords
- polymer
- modified
- acid
- maleamic acid
- olefin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
-
- 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
- C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Olefin polymers modified with substituted maleamic acids are described which modified polymers are useful as metal adhesives.
Olefin polymers modified with substituted maleamic acids are described which modified polymers are useful as metal adhesives.
Description
OLEFIN POLYMER MODIFIED WITH A SUBSTIT~TED
MALEAMIC ACID
This application relates to improved olefin polymers, in particular, olefin polymers modified with maleamic acid derivatives. It also relates to bonded structures of metal and polymeric material.
BACKGROUND OF THE INVENTION
Modification of olefin polymers with unsaturated carboxylic acids produces polymer compositions exhibiting superior adhesion to various substrates, for example, U.S.
Patents 3,483,276 and 3,987 r 122. The improvement of adhesion of elastomers to metal when the elastomer is cured using a free radical curing system in the presence of N-maleamic acids or N-maleimide compounds is also known, U.S. Patent 3,502,542.
However, to realize the full potential for articles of polymeric material bonded to metal, improved adhesion i5 needed.
SUMMARY OF THE INVENTION
It has now been discovered that an alpha monoolefin polymer modified by causing it to react with a substituted maleamic acid, results in a polymer composition exhibiting superio.r adhesion, especially to metal substrates. The modified olefin polymer o~ the invention comprises the reaction product of thermoplas-tic monoolefin polymer and about 0.1 to about 20 weigh-t percent of a substituted maleamic acid of -the :~ormulas O O O
., .. .~
(a) HO-C-C~=CH-C-NH-R-C-OH
in which R is a straight or branched alkylene radical of 1-18 carbon atoms, or O O
ll ll (b) ( HO-C-CH=CH-C-NH-)2 R' n in which n is zero or one, and R' is a straight or branched alkylene radical of 2-18 carbon atoms or arylene of 6-12 carbon atoms. Suitable arylene radicals include phenylene and phenylene substituted by lower alkyl, lower alkoxy or halo, preferably chloro. Lower alkyl is an alkyl radical of 1~6 carbon atoms. Rlkylene radicals oE up to 12 carbon atoms are preEerred~
The modified olefin polymers of the invention may be convenien-tly prepared by melt mixing ole:Ein polymer with substituted maleamic acid, preferably in the presence of a radical generator. Conven-tional plastic masticating equipment such as a mill, Banbury* mixer, or twin screw * Trademark ~ 43-51-1044 mixing extruder may be used to mix the ingredients and to affect reaction. Depending upon the temperature, the type of olefin polymer, substituted maleamic acid and radlcal generator, mixing times of about 1-30 minutes are generally adequate to essentially complete the reaction.
Preferably, the ingredients are caused to~react at a temperature above the melting point of the olefin polymer.
To promote reaction, a (free~ radical generator such as a peroxide is generally present in amounts of about 0.1 to 50 parts per weight per 100 parts by weight of substi-tuted maleamic acid. The amount of radical generator iskept to a minimum to avoid excessive cross-linking of the olefin polymer or, in the case of branched olefin polymers such as polypropylene, to avoid excessive degradation of the polymer. Generally, the amount of radical generator is 5 parts or less, preferably one part or less, by weight per 100 parts by weight of olefin polymer. Pre-ferred modified polymers of the invention comprise the reaction products of olefin polymer and about 0.2 to about 10 percent by weight of the substituted maleamic acid.
Suitable olefin polymers comprise amorphous or crystalline essentially saturated homopolymers or copoly-mers of C2-Cg alpha monoolefins. Thermoplastic crystalline olefin polymers are especially preferred. An important subgroup of satisfactory olefin polymers comprises high molecular weight solid products from the polymerization of monoolefins or mixtures thereof by either high pressure or low pressure processes. Examples of such polymers are the isotactic or syndiotactic monoolefin polymers, repre~
sentative members of which are commonly available. Satis-factory olefins include ethylene, propylene, 1-butene, ~ 43-51-1044A
l-pentene, l-hexene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, and mixtures thereof. Commercially available thermoplastic polyolefin resins, such as, polyethylene, polybutene-l, and polypropylene, or mixtures thereof, may be advantage ously used in the practice of the invention with poly-propylene being preferred. Also suitable for the practice of the invention are copolymers of two or more olefins with copolymers of ethylene and propylene being preferred.
The substituted maleamic acids useful for preparing modified monoolefin polymers of the invention may be named as derivatives of 4-oxo-2-butenoic acid, i.e., 4-(carboxyalkylamino)-4-oxo-2-butenoic acid and 4~4'-(alkanediyldiamino or phenylenediamino)bis-4-oxo-2-butenoic acid. 4,4'-(Hydrazo)bis-4-oxo-2-butenoic acid may also be used to prepare modified polymer. However, for convenience, they shall be named herein as de~ivatives of maleamic acid.
Examples of substituted maleamic acids of Formula (a~
suitable for the practice of this in~ention are:
N-(carboxymethyl)maleamic acid N-(2-carboxyethyl)maleamic acid N-(2-carboxypropyl)maleamic acid N-(3-carboxypropyl)maleamic acid N-(2-carboxybutyl)maleamic acid N-(3-carboxybutyl)maleamic acid N-(4-carboxybutyl)maleamic acid N-(5-carboxypentyl)maleamic acid N-(6-carboxyhexyl)maleamic acid N-(7-carboxyhepyl)maleamic acid N-(8-carboxyoctyl)maleamic acid ~ 43-51-1044A
N-(4-carboxy-1,1,3,3-tetramethylbutyl)maleamic acid N-(10-carboxydecyl)maleamic acid N-(12-carboxydodecyl)maleamic acid N-(15-carboxypentadecyl)maleamic acid N-(18-carboxyoctadecyl)maleamic acid Examples of substituted maleamic acids of Formula (b) suitable for the practice of this invention are:
N, N'-dimaleamic acid N,N'-(dimethylene)dimaleamic acid N,N'~ methyl-1,2-ethanediyl)dimaleamic acid N,N'-(trimethylene)dimaleamic acid N,N'-(l-methyl-1,3-propanediyl)dimaleamic acid N,N'-(tetramethylene)dimaleamic acid N,N'-(2,2-dimethyl-1,3-propanediyl)dimaleamic acid N,N'-(pentame~hylene)dimaleamic acid N, N' -(hexamethylene)dimaleamic acid N,N'-(heptamethylene)dimaleamic acid N,N'-(octamethylene)dimaleamic acid N,N'-(decamethylene)dimaleamic acid N,N'-(dodecamethylene)dimaleamic acid N,N'-(pentadecamethylene)dimaleamic acid N, N'-(octadecylmethylene)dimaleamic acid N,N'-(l, 2-phenylene)dimaleamic acid N,N'-~1,3-phenylene)dimaleamic acid N,N'-(1,4-phenylene)dimaleamic acid N, N'-t4-methyl-1,2-phenylene)dimaleamic acid N,N'-(5-methyl-1,3-phenylene3dimaleamic acid N,N'-t5-methoxy-1,3-phenylene)dimaleamic acid N,N'-(2-chloro-1,4-phenylene)dimaleamic acid N,N'-(5-tert-butyl-1,3-phenylene)dimaleamic acid N,N'-(1,2-naphthylene)dimaleamic acid Any radical generator which promotes the reaction between olefin polymer and substituted maleamic acid is satisfactory for ~he practice of the invention. Suitable radical generators include azides and inorganic or organic peroxides. Examples of satisfactory radical generators are dicumyl peroxide, benzoyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, l,l-bis(t-butylperoxy)-3,3,5-trimethyl cyclohexane, tris-[~ dimethyl-~-(t-butylperoxy) methyl]benzene, di-t-butyl peroxide, lauroyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, ~ bis-(t-butylperoxy)hexane, pinane hydroperoxide, p-menthane hydroperoxide and azobisisobutyronitrile.
One embodiment of the invention comprises reinforced structures comprising a metal member and polymeric material bonded thereto. Enhanced adhesion between the metal and polymeric material is achieved by providing at the inter-face between the metal member and the polymeric material an adhesion enhancing amount of the modified polymer of this invention. The modified olefin polymer of the invention ~ay be applied in the same manner as conventional adhesives, for example, as hot-melt adhesives by direct contact above the softening or melting temperature of the modified polymer or polymeric material containing modified polymer. Thus, the modified polymer can migrate to the interface to form a bond upon cooling. Alternately, the modified polymer may be applied to the surface as a solution or suspension followed by evaporation of the solvent.
Any amount of modified olefin polymer which increases the ~ 43-51-1044A
adhesion between the metal and the polymeric material is satisfactory for making the improved structures of the invention. The amoun~ required varies depending upon the type of metal and type of polymeric material involved.
However, the amount is readily ascertained by trial within the skill of the art. The amount is incrementally increased wltil sufficient adhesion is achieved. It is understood that reinforced structures of the invention include composites, laminates and articles in which the metal member is in the form of a sheet or continuous or discontinuous fiber. The term "polymeric material"
includes any unchanged olefin polymer remaining a~ter a portion of the olefin polymer has been modified by reaction with substituted maleamic acid.
Polymeric material other than olefin polymer suitable for making bonded metal structures include any polymer which the modified olefin polymer of the invention will adhere to metal. Examples of sa~isfactory polymeric materials include nylons, polyesters, polyurethanes, styrene-acrylonitrile resins, polystyrene, ABS resins, and cured or uncured rubber. Preferred polymeric materials comprise olefin polymers especially polyethylene and polypropylene, and their blends with cured or uncured rubber.
Any metal member is suitable for making structures of the invention but particularly suited are those metals exhibiting a valence state of two or more and a melting temperature above 200C. Preferred metal members are selected from the group consisting of iron, aluminum, zinc, copper, and their alloys, such as brass and steel, with aluminum being especially preferred.
~ 43-51-1044A
It is generally required that the adhesive layer, the bonding surface of the metal substrate and the other substrate, if present, be heated above the melting or softening temperature of the adhesive.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
_ Polypropylene is modified by the action of a substi-tuted maleamic acid in the presence of a free radical generator. For example, one hundred parts by weight of polypropylene !Profax 6723, melt flow 0.8, ASTM D-1238, cond. L) and 5 part5 by weight of the indicated reactants are masticated at 80 rpm in a Brabende~ mixer at about 180C. After a homogeneous mixture is obtained, 0.~6 parts by weight of a radical generator, 2,5-dimethyl-2,5-bis(t-butylper~xy)hexane, Lupersol-lO1*, is added and mixing is continued for about 5 minutes. The modified polypropylene is removed, cooled in a press and evaluated as a hot-melt adhesive either neat or blended with other materials.
A reinforced structure is formed by bonding two 5 mil. thick aluminum sheets (5" x 5" square) together with about l gram of modified polypropylene or blend thereof.
An aluminum sandwich comprising the two aluminum sheets bonded by the modified polypropylene is formed by pressing, at 210C and at a pressure sufficient to give a polymeric interlayer about 5 mils thick. The sandwich ls cut into one inch strips. The force required to pull the two aluminum strips apart at 180 is measured with a tensile tester using a separation speed of lO inches per minute.
The adhesion values are recorded in pounds per linear inch, pli. The adhesion of aluminum to neat modified-* Trade Marks ~ 43-51-1044A
_g_ polymer designated modified PP and to a blend with thermo-plastic elastomeric composition designated TE/PP blend is evaluated.
The thermoplastic elastomeric composition is prepared by dynamic vulcanization as described in U~ S. Patent 4,130,535, except part of the polypropylene is replaced by modified polypropylene and a phenolic curative is used. The thermoplastic elastomeric composition comprises (all parts by weight) 50 parts of EPDM rubber (Epsyn 70A), 37.5 parts of polypropylene (Proax 6723)* and 12.5 parts of modified polypropyleneO Five parts of phenolic curing resin, SP-1045, and one part of cure activator, zinc oxide are used to cure the rubber.
The results are shown in Table 1. Stocks 1, 2, and 3 are controls where the reactants are maleic acid, maleic anhydride, and 1,3-phenylenebismaleimide, respectively.
Stocks 4-7 illustrate polypropylene modified with dimale-amic acid derivatives. ~tocks 8 and 9 illustrate poly-propylene modified with N-carboxyalkyl maleamic acids.
The data show that polypropylene modified with a dimaleamic acid derivative gives superior adhesion when used as a neat material and that polypropylene modified with an N-carboxyalkyl maleic acid gives superior adhesion in a thermoplastic elastomer blend. Stock 4 is repeated except only 2 parts, instead of 5 parts, or N,N'-(hexamethylene) dimaleamic acid is used with the polypropylene. The adhesion values are 6.7 pli for modified PP and 8.0 pli for the TE/PP blend.
Other modified polypropylene compositions are prepared and tested as in Table 1, except the polypropylene is Profax 6523 (melt index 4) and 1.4~ parts of the radical ~enerator are used. The results are shown in Table 2.
* I'rade Marks Unable to recognize this page.
~ 43-51-1044~
ALUMINUM
ADHESION, pli STOCK NO. REACTANT TE/PP BLEMD
1 N-(carboxymethyl)maleamic 23.5 acid
MALEAMIC ACID
This application relates to improved olefin polymers, in particular, olefin polymers modified with maleamic acid derivatives. It also relates to bonded structures of metal and polymeric material.
BACKGROUND OF THE INVENTION
Modification of olefin polymers with unsaturated carboxylic acids produces polymer compositions exhibiting superior adhesion to various substrates, for example, U.S.
Patents 3,483,276 and 3,987 r 122. The improvement of adhesion of elastomers to metal when the elastomer is cured using a free radical curing system in the presence of N-maleamic acids or N-maleimide compounds is also known, U.S. Patent 3,502,542.
However, to realize the full potential for articles of polymeric material bonded to metal, improved adhesion i5 needed.
SUMMARY OF THE INVENTION
It has now been discovered that an alpha monoolefin polymer modified by causing it to react with a substituted maleamic acid, results in a polymer composition exhibiting superio.r adhesion, especially to metal substrates. The modified olefin polymer o~ the invention comprises the reaction product of thermoplas-tic monoolefin polymer and about 0.1 to about 20 weigh-t percent of a substituted maleamic acid of -the :~ormulas O O O
., .. .~
(a) HO-C-C~=CH-C-NH-R-C-OH
in which R is a straight or branched alkylene radical of 1-18 carbon atoms, or O O
ll ll (b) ( HO-C-CH=CH-C-NH-)2 R' n in which n is zero or one, and R' is a straight or branched alkylene radical of 2-18 carbon atoms or arylene of 6-12 carbon atoms. Suitable arylene radicals include phenylene and phenylene substituted by lower alkyl, lower alkoxy or halo, preferably chloro. Lower alkyl is an alkyl radical of 1~6 carbon atoms. Rlkylene radicals oE up to 12 carbon atoms are preEerred~
The modified olefin polymers of the invention may be convenien-tly prepared by melt mixing ole:Ein polymer with substituted maleamic acid, preferably in the presence of a radical generator. Conven-tional plastic masticating equipment such as a mill, Banbury* mixer, or twin screw * Trademark ~ 43-51-1044 mixing extruder may be used to mix the ingredients and to affect reaction. Depending upon the temperature, the type of olefin polymer, substituted maleamic acid and radlcal generator, mixing times of about 1-30 minutes are generally adequate to essentially complete the reaction.
Preferably, the ingredients are caused to~react at a temperature above the melting point of the olefin polymer.
To promote reaction, a (free~ radical generator such as a peroxide is generally present in amounts of about 0.1 to 50 parts per weight per 100 parts by weight of substi-tuted maleamic acid. The amount of radical generator iskept to a minimum to avoid excessive cross-linking of the olefin polymer or, in the case of branched olefin polymers such as polypropylene, to avoid excessive degradation of the polymer. Generally, the amount of radical generator is 5 parts or less, preferably one part or less, by weight per 100 parts by weight of olefin polymer. Pre-ferred modified polymers of the invention comprise the reaction products of olefin polymer and about 0.2 to about 10 percent by weight of the substituted maleamic acid.
Suitable olefin polymers comprise amorphous or crystalline essentially saturated homopolymers or copoly-mers of C2-Cg alpha monoolefins. Thermoplastic crystalline olefin polymers are especially preferred. An important subgroup of satisfactory olefin polymers comprises high molecular weight solid products from the polymerization of monoolefins or mixtures thereof by either high pressure or low pressure processes. Examples of such polymers are the isotactic or syndiotactic monoolefin polymers, repre~
sentative members of which are commonly available. Satis-factory olefins include ethylene, propylene, 1-butene, ~ 43-51-1044A
l-pentene, l-hexene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, and mixtures thereof. Commercially available thermoplastic polyolefin resins, such as, polyethylene, polybutene-l, and polypropylene, or mixtures thereof, may be advantage ously used in the practice of the invention with poly-propylene being preferred. Also suitable for the practice of the invention are copolymers of two or more olefins with copolymers of ethylene and propylene being preferred.
The substituted maleamic acids useful for preparing modified monoolefin polymers of the invention may be named as derivatives of 4-oxo-2-butenoic acid, i.e., 4-(carboxyalkylamino)-4-oxo-2-butenoic acid and 4~4'-(alkanediyldiamino or phenylenediamino)bis-4-oxo-2-butenoic acid. 4,4'-(Hydrazo)bis-4-oxo-2-butenoic acid may also be used to prepare modified polymer. However, for convenience, they shall be named herein as de~ivatives of maleamic acid.
Examples of substituted maleamic acids of Formula (a~
suitable for the practice of this in~ention are:
N-(carboxymethyl)maleamic acid N-(2-carboxyethyl)maleamic acid N-(2-carboxypropyl)maleamic acid N-(3-carboxypropyl)maleamic acid N-(2-carboxybutyl)maleamic acid N-(3-carboxybutyl)maleamic acid N-(4-carboxybutyl)maleamic acid N-(5-carboxypentyl)maleamic acid N-(6-carboxyhexyl)maleamic acid N-(7-carboxyhepyl)maleamic acid N-(8-carboxyoctyl)maleamic acid ~ 43-51-1044A
N-(4-carboxy-1,1,3,3-tetramethylbutyl)maleamic acid N-(10-carboxydecyl)maleamic acid N-(12-carboxydodecyl)maleamic acid N-(15-carboxypentadecyl)maleamic acid N-(18-carboxyoctadecyl)maleamic acid Examples of substituted maleamic acids of Formula (b) suitable for the practice of this invention are:
N, N'-dimaleamic acid N,N'-(dimethylene)dimaleamic acid N,N'~ methyl-1,2-ethanediyl)dimaleamic acid N,N'-(trimethylene)dimaleamic acid N,N'-(l-methyl-1,3-propanediyl)dimaleamic acid N,N'-(tetramethylene)dimaleamic acid N,N'-(2,2-dimethyl-1,3-propanediyl)dimaleamic acid N,N'-(pentame~hylene)dimaleamic acid N, N' -(hexamethylene)dimaleamic acid N,N'-(heptamethylene)dimaleamic acid N,N'-(octamethylene)dimaleamic acid N,N'-(decamethylene)dimaleamic acid N,N'-(dodecamethylene)dimaleamic acid N,N'-(pentadecamethylene)dimaleamic acid N, N'-(octadecylmethylene)dimaleamic acid N,N'-(l, 2-phenylene)dimaleamic acid N,N'-~1,3-phenylene)dimaleamic acid N,N'-(1,4-phenylene)dimaleamic acid N, N'-t4-methyl-1,2-phenylene)dimaleamic acid N,N'-(5-methyl-1,3-phenylene3dimaleamic acid N,N'-t5-methoxy-1,3-phenylene)dimaleamic acid N,N'-(2-chloro-1,4-phenylene)dimaleamic acid N,N'-(5-tert-butyl-1,3-phenylene)dimaleamic acid N,N'-(1,2-naphthylene)dimaleamic acid Any radical generator which promotes the reaction between olefin polymer and substituted maleamic acid is satisfactory for ~he practice of the invention. Suitable radical generators include azides and inorganic or organic peroxides. Examples of satisfactory radical generators are dicumyl peroxide, benzoyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, l,l-bis(t-butylperoxy)-3,3,5-trimethyl cyclohexane, tris-[~ dimethyl-~-(t-butylperoxy) methyl]benzene, di-t-butyl peroxide, lauroyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, ~ bis-(t-butylperoxy)hexane, pinane hydroperoxide, p-menthane hydroperoxide and azobisisobutyronitrile.
One embodiment of the invention comprises reinforced structures comprising a metal member and polymeric material bonded thereto. Enhanced adhesion between the metal and polymeric material is achieved by providing at the inter-face between the metal member and the polymeric material an adhesion enhancing amount of the modified polymer of this invention. The modified olefin polymer of the invention ~ay be applied in the same manner as conventional adhesives, for example, as hot-melt adhesives by direct contact above the softening or melting temperature of the modified polymer or polymeric material containing modified polymer. Thus, the modified polymer can migrate to the interface to form a bond upon cooling. Alternately, the modified polymer may be applied to the surface as a solution or suspension followed by evaporation of the solvent.
Any amount of modified olefin polymer which increases the ~ 43-51-1044A
adhesion between the metal and the polymeric material is satisfactory for making the improved structures of the invention. The amoun~ required varies depending upon the type of metal and type of polymeric material involved.
However, the amount is readily ascertained by trial within the skill of the art. The amount is incrementally increased wltil sufficient adhesion is achieved. It is understood that reinforced structures of the invention include composites, laminates and articles in which the metal member is in the form of a sheet or continuous or discontinuous fiber. The term "polymeric material"
includes any unchanged olefin polymer remaining a~ter a portion of the olefin polymer has been modified by reaction with substituted maleamic acid.
Polymeric material other than olefin polymer suitable for making bonded metal structures include any polymer which the modified olefin polymer of the invention will adhere to metal. Examples of sa~isfactory polymeric materials include nylons, polyesters, polyurethanes, styrene-acrylonitrile resins, polystyrene, ABS resins, and cured or uncured rubber. Preferred polymeric materials comprise olefin polymers especially polyethylene and polypropylene, and their blends with cured or uncured rubber.
Any metal member is suitable for making structures of the invention but particularly suited are those metals exhibiting a valence state of two or more and a melting temperature above 200C. Preferred metal members are selected from the group consisting of iron, aluminum, zinc, copper, and their alloys, such as brass and steel, with aluminum being especially preferred.
~ 43-51-1044A
It is generally required that the adhesive layer, the bonding surface of the metal substrate and the other substrate, if present, be heated above the melting or softening temperature of the adhesive.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
_ Polypropylene is modified by the action of a substi-tuted maleamic acid in the presence of a free radical generator. For example, one hundred parts by weight of polypropylene !Profax 6723, melt flow 0.8, ASTM D-1238, cond. L) and 5 part5 by weight of the indicated reactants are masticated at 80 rpm in a Brabende~ mixer at about 180C. After a homogeneous mixture is obtained, 0.~6 parts by weight of a radical generator, 2,5-dimethyl-2,5-bis(t-butylper~xy)hexane, Lupersol-lO1*, is added and mixing is continued for about 5 minutes. The modified polypropylene is removed, cooled in a press and evaluated as a hot-melt adhesive either neat or blended with other materials.
A reinforced structure is formed by bonding two 5 mil. thick aluminum sheets (5" x 5" square) together with about l gram of modified polypropylene or blend thereof.
An aluminum sandwich comprising the two aluminum sheets bonded by the modified polypropylene is formed by pressing, at 210C and at a pressure sufficient to give a polymeric interlayer about 5 mils thick. The sandwich ls cut into one inch strips. The force required to pull the two aluminum strips apart at 180 is measured with a tensile tester using a separation speed of lO inches per minute.
The adhesion values are recorded in pounds per linear inch, pli. The adhesion of aluminum to neat modified-* Trade Marks ~ 43-51-1044A
_g_ polymer designated modified PP and to a blend with thermo-plastic elastomeric composition designated TE/PP blend is evaluated.
The thermoplastic elastomeric composition is prepared by dynamic vulcanization as described in U~ S. Patent 4,130,535, except part of the polypropylene is replaced by modified polypropylene and a phenolic curative is used. The thermoplastic elastomeric composition comprises (all parts by weight) 50 parts of EPDM rubber (Epsyn 70A), 37.5 parts of polypropylene (Proax 6723)* and 12.5 parts of modified polypropyleneO Five parts of phenolic curing resin, SP-1045, and one part of cure activator, zinc oxide are used to cure the rubber.
The results are shown in Table 1. Stocks 1, 2, and 3 are controls where the reactants are maleic acid, maleic anhydride, and 1,3-phenylenebismaleimide, respectively.
Stocks 4-7 illustrate polypropylene modified with dimale-amic acid derivatives. ~tocks 8 and 9 illustrate poly-propylene modified with N-carboxyalkyl maleamic acids.
The data show that polypropylene modified with a dimaleamic acid derivative gives superior adhesion when used as a neat material and that polypropylene modified with an N-carboxyalkyl maleic acid gives superior adhesion in a thermoplastic elastomer blend. Stock 4 is repeated except only 2 parts, instead of 5 parts, or N,N'-(hexamethylene) dimaleamic acid is used with the polypropylene. The adhesion values are 6.7 pli for modified PP and 8.0 pli for the TE/PP blend.
Other modified polypropylene compositions are prepared and tested as in Table 1, except the polypropylene is Profax 6523 (melt index 4) and 1.4~ parts of the radical ~enerator are used. The results are shown in Table 2.
* I'rade Marks Unable to recognize this page.
~ 43-51-1044~
ALUMINUM
ADHESION, pli STOCK NO. REACTANT TE/PP BLEMD
1 N-(carboxymethyl)maleamic 23.5 acid
2 N-(10-carboxydecyl)maleamic 13.5 acid Enhancing adhesion by blending uncured rubber and modified polypropylene of the invention is illustrated in Table 3. The modified polypropylene is prepared with Profax 6523 polypropylene by the same procedure as above. In Stocks l-S, five parts of N-(carboxymethyl)-malaamic acid (CMMA) and 1.48 parts of organic peroxide (L-101) are used per 100 parts of polypropylene. In Stocks 6-7, ten parts of N-(carboxymethyl)maleamic acid and 0.87 parts of organic peroxide (L-101) are used per 100 parts of polypropylene. In Stocks 8-11, there are brought into reaction, 5 parts of N,N-(hexamethylene) dimaleamic acid (HMDMA) and 0.56 parts of organic peroxide with 100 parts of polypropylene. In Stocks 1~-13, 5 parts of N,N'-(1,4-phenylene)dimaleamic acid (PDMA) and 0.56 parts of organic peroxide are used per 100 parts of polypropylene. The modified polypropylene is mixed with uncured EPDM rubber (ethylene-propylene-norbornene terpolymer, Epsyn 70A) in a Brabender mixer above the melting temperature of the polypropylene in the proportions indicated (all parts by weight). Aluminum sandwiches are prepared as above by pressing the adhesive compositions between pairs of heated sheets of aluminum foil. Adhesion is measured as before. The results show 43~51-1044A
ALUMINUM
MODIFIED PP EPDM RUBBER ADHESION, STOCK NO. MODIFIER (parts by weight) _ pli 1 CMMA 100 - <0.5
ALUMINUM
MODIFIED PP EPDM RUBBER ADHESION, STOCK NO. MODIFIER (parts by weight) _ pli 1 CMMA 100 - <0.5
3 CMMA 70 30 10.0
4 CMMA 40 60 8.5 C~MA 20 80 6.5 6 CMMA 100. - 9.0 7 CMMA 70* 30 32.5 8 HMDMA 100 - 6.0 9 HMDMA 80 20 10.0 HMDMA 70 30 14.5 11 HMDMA 60 40 12.5 12 PDMA 100 - 11.0 13 PDMA 70 30 26.0 *Blend of 25 parts of modif ied PP and 75 parts of unmodif ied PP .
1~3~ 43-51-1044A
that the incorporation of uncured rubber into the modified-polypropylene substantially increases the adhesion to aluminum. The data further indicates that superior adhesion is achieved when the proportion of rubber is about 30 parts by weight per lO0 parts by weight of poly-propylene, modified polypropylene and uncured rubbercombined.
Although the inven-tion has been illustrated by typical examples, it is not limited thereto. Changes and modifications of the examples of the invention herein chosen for purposes of disclosure can be made which do not constitute departure from the spirit and scope of the invention.
1~3~ 43-51-1044A
that the incorporation of uncured rubber into the modified-polypropylene substantially increases the adhesion to aluminum. The data further indicates that superior adhesion is achieved when the proportion of rubber is about 30 parts by weight per lO0 parts by weight of poly-propylene, modified polypropylene and uncured rubbercombined.
Although the inven-tion has been illustrated by typical examples, it is not limited thereto. Changes and modifications of the examples of the invention herein chosen for purposes of disclosure can be made which do not constitute departure from the spirit and scope of the invention.
Claims (23)
1. A modified olefin polymer comprising the reaction product of thermoplastic monoolefin polymer and about 0.1 to about 20 weight percent of a substituted maleamic acid of the formulas (a) in which R is a straight or branched alkylene radical of 1-18 carbon atoms, or (b) in which n is zero or one, and R' is a straight or branched alkylene radical of 2-18 carbon atoms or arylene of 6-12 carbon atoms.
2. The polymer of Claim 1 in which the olefin polymer is a thermoplastic essentially saturated homopolymer or copolymer of a C2-C8 alpha-olefin.
3. The polymer of Claim 2 comprising the reaction product of about 0.2 to about 10 weight percent of a substituted maleamic acid of Formula (a).
4. The polymer of Claim 2 comprising the reaction product of about 0.2 to about 10 weight percent of a substituted maleamic acid of Formula (b) in which n is one.
5. The polymer of Claim 3 in which the olefin polymer is crystalline polypropylene.
6. The polymer of Claim 4 in which the olefin polymer is crystalline polypropylene.
7. The polymer of Claim 5 in which R is an alkylene radical of 1-12 carbon atoms.
8. The polymer of Claim 6 in which R' is an alkylene radical of 2-12 carbon atoms.
9. The polymer of Claim 6 in which R' is 1,3-phenylene.
10. The polymer of Claim 6 in which R' is 1,4-phenylene.
11. The polymer of Claim 7 in which R is methylene.
12. The polymer of Claim 8 in which R' is hexa-methylene.
13. In a structure comprising a metal member and a polymeric material bonded thereto, the improvement comprises, providing at the interface between the metal member and the polymeric material, an adhesive comprising an adhesion enhancing amount of the modified polymer of Claim 1.
14. The structure of Claim 13 in which the metal member is iron, aluminum, zinc, copper, or alloys thereof.
15. The structure of Claim 14 in which the polymeric material comprises olefin polymer.
16. The structure of Claim 14 in which the polymeric material comprises rubber.
17. The structure of Claim 16 in which the rubber is EPDM rubber.
18. The structure of Claim 15 in which the olefin polymer is polypropylene.
19. The structure of Claim 18 in which the metal is aluminum.
20. The structure of Claim 16 in which the adhesive is the modified polymer of Claim 7.
21. The structure of Claim 14 in which the adhesive is the modified polymer of Claim 8.
22. The structure of Claim 14 in which R' is phenylene.
23. The polymer of claim 1 comprising the reaction product of said monoolefin polymer, said maleamic acid and 0.1 to 50 parts by weight of a radical generator per 100 parts by weight of substituted maleamic acid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12861180A | 1980-03-10 | 1980-03-10 | |
| US128,611 | 1980-03-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1183991A true CA1183991A (en) | 1985-03-12 |
Family
ID=22436159
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000372597A Expired CA1183991A (en) | 1980-03-10 | 1981-03-09 | Olefin polymer modified with a substituted maleamic acid |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS56143204A (en) |
| BE (1) | BE887852A (en) |
| CA (1) | CA1183991A (en) |
| DE (1) | DE3108895A1 (en) |
| GB (1) | GB2071110B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4433114A (en) * | 1981-11-17 | 1984-02-21 | Monsanto Company | Diene rubber and method and composition for rubber treatment |
| US4376189A (en) * | 1981-11-17 | 1983-03-08 | Monsanto Company | Rubber compositions and method of treating rubber |
| DE10050253A1 (en) * | 2000-10-11 | 2002-04-25 | Hueck Folien Gmbh & Co Kg | composite film |
| EP1492665A1 (en) * | 2002-04-11 | 2005-01-05 | Hueck Folien GmbH & Co. KG | Dry lamination method using non-reactive, monomer-free lamination adhesives |
-
1981
- 1981-03-09 CA CA000372597A patent/CA1183991A/en not_active Expired
- 1981-03-09 JP JP3372381A patent/JPS56143204A/en active Pending
- 1981-03-09 GB GB8107335A patent/GB2071110B/en not_active Expired
- 1981-03-09 BE BE0/204053A patent/BE887852A/en not_active IP Right Cessation
- 1981-03-09 DE DE19813108895 patent/DE3108895A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| DE3108895A1 (en) | 1982-02-18 |
| DE3108895C2 (en) | 1989-12-28 |
| JPS56143204A (en) | 1981-11-07 |
| BE887852A (en) | 1981-09-09 |
| GB2071110B (en) | 1984-08-08 |
| GB2071110A (en) | 1981-09-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4725637A (en) | Process for the production of a thermoplastic elastomer composition | |
| CA1243794A (en) | Thermoplastic elastomer composition | |
| EP0827994B1 (en) | Use of grafted amorphous poly-alfa-olefins as moisture-curable raw material for adhesives and as adhesives | |
| US5698617A (en) | Concentrates suitable for the preparation of functionalized polyolefins and functionalization process using said concentrates | |
| EP0124247B1 (en) | Modified polyolefin composition useful for bonding materials | |
| KR910005563B1 (en) | Maleic anhydrine grafts of olefin polymers | |
| JP3464314B2 (en) | Polyolefin composition suitable for high-frequency sealable sheets and films | |
| CA1336627C (en) | Moulding compound made of elastomeric polyolefin rubbers, polyethylene and/or ethylene copolymers and additives, and elastic sealing strips made therefrom | |
| CA1333827C (en) | Grafting polyolefin blends and use of the graft copolymer blend as an adhesion promoter and for the preparation of ionomers | |
| US4374956A (en) | Olefin polymer modified with substituted maleamic acid | |
| US4350740A (en) | Modified olefin polymers | |
| GB1566495A (en) | Synergistically adhesive blends of graft copolymer and polyolefin resins | |
| CA1183991A (en) | Olefin polymer modified with a substituted maleamic acid | |
| EP0115434A2 (en) | Semicrystalline ethylene alpha-olefin copolymers for hot melt adhesives | |
| JPS6232233B2 (en) | ||
| WO1991017192A1 (en) | Modified polyolefin polymer, production thereof, and resin composition containing the same | |
| JPH11501338A (en) | Grafted propylene homo- and copolymers and their preparation | |
| KR940004166B1 (en) | Modified polyoleffine-adhesive compositions | |
| JPS608347A (en) | Adhesive polypropylene composition | |
| JP4905868B2 (en) | Ethylene propylene diene rubber composition and ethylene propylene diene rubber-plastic composite | |
| JPS5849736A (en) | Polyolefin composition | |
| KR0163984B1 (en) | Method of manufacturing thermoplastic elastomers | |
| JPS59221347A (en) | Thermoplastic elastomer composition having excellent injection weldability | |
| RU2132345C1 (en) | Reinforced thermoplastic polyolefin composition | |
| CA1322798C (en) | Impact resistant blends of thermoplastic polyamides, polyolefins and elastomers and process for the preparation thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry | ||
| MKEX | Expiry |
Effective date: 20020312 |