CA1050363A - Copolymers of ethylene process for producing them and their use - Google Patents
Copolymers of ethylene process for producing them and their useInfo
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- CA1050363A CA1050363A CA237,321A CA237321A CA1050363A CA 1050363 A CA1050363 A CA 1050363A CA 237321 A CA237321 A CA 237321A CA 1050363 A CA1050363 A CA 1050363A
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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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract
ABSTRACT OF THE DISCLOSURE
This invention relates to novel quaternary co-polymers and their preparation. The quaternary copolymers consist of 70-90 parts ethylene, 0.5-15 parts of an alkyl ester (wherein said alkyl group contains up to 8 carbon atoms) of an unsaturated monocarboxylic acid having 3-6 carbon atoms or a vinyl ester of a saturated monocarboxylic acid having up to 3 carbon atoms, 0.5-10 parts of an amide of an unsaturated monocarboxylic acid having 3-6 carbon atoms, and 0.1-5 parts of a vinyl ether having up to 10 carbon atoms; the sum of the parts totalling 100.
This invention relates to novel quaternary co-polymers and their preparation. The quaternary copolymers consist of 70-90 parts ethylene, 0.5-15 parts of an alkyl ester (wherein said alkyl group contains up to 8 carbon atoms) of an unsaturated monocarboxylic acid having 3-6 carbon atoms or a vinyl ester of a saturated monocarboxylic acid having up to 3 carbon atoms, 0.5-10 parts of an amide of an unsaturated monocarboxylic acid having 3-6 carbon atoms, and 0.1-5 parts of a vinyl ether having up to 10 carbon atoms; the sum of the parts totalling 100.
Description
This invention relates to quaternary copolymers containing ethylene as the main constituent. Combined with the ethylene are an ester of an unsaturated carboxylic acid and a saturated alcohol or a vinyl ester of a saturated carboxylic acid, the amide of an unsaturated carboxylic acid, and an alkyl vinyl ether.
German published Patent Application DAS 1,645,018 describes the copolymerization of ethylene with tert-butylamino ethyl methacrylate or an ester of an unsatura-ted carboxylic acid, and the amide of an unsaturated carboxylic acid to produce copolymers useful for the pro-duction of hollow-shaped articles and film. These articles can be produced by the usual methods, such as casting, ex-trusion and injection molding.
. -2-:1~50363 German published Patent Application DAS 1,645,024 relates to a process for producing ethylene copolymers con-taining from 1-10 mole percent of a vinyl ether, from 0.5-20 mole percent o~ unsubstituted acryl or methacrylamides and 70-98.5 mole percent of ethylene.
German Patent Application P 24 00 978.7 of the present inventors, which has not yet been published, teaches a process for bonding together or coating materials using as an adhesive or coating composition, an olefin copolymer.
This copolymPr contains 70-90 parts of ethylene, ~.5-10 parts of the amide of an e~hy~enically unsaturated carboxylic acid and 0.5-20 parts of the ester of an ethylenically un-saturated carboxylic acid. When producing polymers having the~oomposition mentioned above,it is necessary, to achieve commercially useful melt flow indices, to maintain high modifier concentrations. For example, the polymerization is ef~ected in the presence of 10-12 percent of propane as a modifying ingredient. This percentage is based on the weight of ethylene. This substantial dilution of the ethylene results in a marked reduction in conversion. Such high concentrations of modifier are not necessary in the process according to the present invention because the vinyl ether has a molecular weight-controlling action. In addition, the adhesive properties of these polymers are largely dependent upon their composition. Maximum adhesive strength is achieved only within a very narrow concentration ~ 50363 range of the comonomers. Therefore, it is necessary when producing the polymer that the individual components are maintained in the precise proportion requi.red.
The prior art also shows the use of binary and tertiary ethylene copolymers containing acrylic acid for bonding and coating various materials and substrates.
These high molecular weight compounds also exhibit inherent deficiencies which are due to the presence of carboxyl groups in the macromolecule. Because of the formation of hydrogen bridges, the carboxyl groups favor the accumu-lation of water between the coating and the substrate.
This results in delamination and detachment of the polymer from the substrate. This phenomenon is particularly serious in cases in which the bonding m~çhanism is based on the carbo~lic acid groups of the adhesion promoter; for example, when the copolymers adhere to metals.
It has now been found that the deficiencies and disadvantages mentioned above are not exhibited by the quat-ernary copolymers o~ the present invention. These copolymers consis~ of 70-90 parts of ethylene, 0.5-15 parts of an alkyl ester (wherein the alkyl group contains up to 8 carbon atoms) of an unsaturated monocarboxylic acid having 3-6 carbon atoms or the vinyl ester of a saturated monocarboxylic acid having up to 3 carbon atoms, 0.5-10 parts of an amide of an unsaturated monocarboxylic acid having 3-6 carbon atoms, and 0.1-5 parts of a vinyl ether having up to 10 carbon atoms; the sum of the parts totalling 100 ~LOS~363 It is a preferred embodlment of this invention that the quaternary copolymers contain 80-90 parts of ethy-lene, 7-12 parts of an alkyl ester (wherein the alkyl group contains up to 8 carbon!atoms) oE an unsaturated monocarboxy-lic acid or a vinyl es~er of a sa~urated monocarboxylic acid having up to 3 carbon atoms, 5-8 parts of an amide of an unsaturated carboxylic acid having 3-6 carbon atoms and 0.1-1 part of an aliphatic or aromatic vinyl ether having up to 10 carbon atoms; the sum of the parts totalling 100.-The above-mentioned quaternary copolymers are characterized by crystalline melting points of 95C.-100C.
and densities of 0.925-0.938, measured acco~ding to DIN 53 479.
Products having melt flow index values of 0.1-100, especially those having melt flow index values between 1 and 50 are suitable as adhesives. As compared with terpolymers of ethylene, acrylic acid and acrylic acid esters, the quater-nary copolymers have a higher modulus of elasticity.
Examples of esters of unsaturated carboxylic acids which may be used as comonomers include ethyl acrylate, n-propyl acrylate, n-butyl acrylate, tert-butyl acrylate, t~rt-butyl methacrylate, tert-butyl crotonate, and 2-ethyl hexyl acrylate. Particularly suitable are the es~ers of acrylic and methacrylic acids with tert-butanol and tert-amyl alcohol. Vinyl acetate is representative of the vinyl esters of saturated carboxylic acids.
For the purposes of this invention, acrylamide, methacrylamide and crotonic acid amide are the preferred i~5~363 amides of unsaturated carboxylic a~ids.
Examples of copolymerizable ethers include methyl ~inyl ether, ethyl vinyl ether, propyl vinyl ether, i-butyl vinyl etherS and n-butyl vinyl ether. The type of the ether used does not affect the adhesiveness of the copolymer.
The copolymers according to the present invention are produced at pressures of 400 to 4,000 bars and ~empera-tures of 100C. to 350C. The polymerization is carried out in the presence of catalytic quantiti~s of free radical initiators (e.g. oxygen, in amounts of 2 to 250 molar parts per million parts of ethylene). Furthermore, peroxides and other free radical forming substances, such as tert-butyl perbenzoate, dilauryl peroxide, didecanoyl peroxide, di-tert-butyl peroxide, azoisobutyrodinitrile may be used alone or in mixture in amounts of 2 to 200 molar parts per million parts of ethylene. The polymerization may be effec~ed in the presence of modifying ingredients such as aliphatic alcohols, aliphatic saturated carbonyl compounds, chlorinated hydrocarbons and hydrogen. The process according to this invention may be effected either continuously or batch-wise; the continuous operation is preferred. When operating continuously, the copolymer is withdrawn ~r~m the reactor.
The unreacted portion of the monomers, the initiator and the modifying ingredients are then recycled.
The quaternary copolymers prepared according to the present invention, which contain 0.1 to 1.0% of an alkyl ~(~5~336~
vinyl ether, exhibit excellent adhesive strength on various substrates such as metals and woods. This adhesive strength is maintained at a high level regardless of the ratio of the other comonomers.
The copolymers strongly adhere to the substrate as coatings, impregnations and surface layers, especially if applied in the molten state. The copolymers may be used in this manner as thermal plastic adhesives for metalsg ceramic materials, paper, textiles, wood, glass, leather and plastic materials.
~ue to the presence of hydrophilic amide groups, ~he quaternary polymers may also be processed to produce stable emulsions which permit the use of the polymers in ~inely divided form. When used in the form of emulsions and solutions of the copolymers, it is possible to produce very thin films on metals, ceramic materials, glass, tex-~iles, wood, paper, leather, and plastic materials These films are useful as adhesives for lamination with polyole-fins such as polyethylene or rubber.
A surprising result of the present invention is that a smaller amount of an alkyl ester of an unsaturated carboxylic acid is needed than that which would be ex-pected to obtain satisfactory adhesive strength. This result is shown even when the copolymer contains only a small amount of an alkyl ether.
~1~50363 The polymers or the materials that are impreg-nated with the polymers can be printed. Their affinity with dyes is remarkable. In addition, the copolymers are useful as additives in coating compositions, especially those polymers which con~ain a relatively high proportion of copolymerized comonomers.
The following examples illustrate the production of the new polymers and their use for bonding or coating substrates and materials In these examples, parts and percentages are by weight unless otherwis~ stated.
A. Production of the polymers The quaternary copolymers are produced in a con-tinuously operated laboratory autoclave unit, comprising an autoclave equipped with a magnetic stirrer and an electrical heater. Before it is introduced into the auto-clave, the ethylene is mixed with gaseous additives such as oxygen as an initiator and, if necessary or desired, propane as a modifier. The mixture is then compressed to the reaction pressure. The reaction mixture is then passed through a preheater and into the autoclave. At ~he same time, the comonomers, if necessary, are dissolved or diluted and are then fed into the reactor by means o two high pressure metering pumps having different delîveries. Low molecular weight polar organic compounds such as methanol, ethanol and butanol have been found ~ ~S~ 3 ~ 3 to be particularly useful solvents. The polymerization is effected at temperatures between 170C. and 280C.
The~polymer-monomer mixture leaving the reactor is de-pressurized to about 2 to 3 bars by means of a cont~ol valve. In doing so, the polymer formed is separated and collected in alternately filled receivers.
B. Determination of adhesive strength Cleaned aluminum strips o 100 mm. in length, 100 mm. in width and 1.5 mm. in thickness were bonded to-gether by pressing (pressure, 3 kgs./sq.cm.; pressing time, 30 to 40 seconds; compression temperature 180C.) over a length of 70 mm. by means of films consisting of the particular ethylene copolymers and produced by compression or e~trusion through a slot die. In another experiment9 aluminum strips having the same dimensions were bonded under the same conditions to a sheet of high pressure poly-ethylene of 4 mm. thickness. The unbonded lengths of the aluminum strips were bent at right angles in opposite dire~tions.
The adhesive properties are primarily demonstrated by the peel strength. This value represents the force per tear length which is necessary to braak the bond. With respect to the adhesive property, it is necessary to dif-ferentiate between the force required to initiate peeling and the force required to maintain peeling per tear length.
~ OS0363 The force to maintain peeling is important in determining the adhesive strength of ~he product being tested.
The physical data mentioned above is de~ermined by means of a tensile tester. Metal sheets (30 mm. by 100 mm.) are bent at an angle and are placed in the grippers of the testing machine in such a manner th~t the adhesive coated surface (70 mm. by 100 mm.) extends at right angles with respect to grippers. The system is pulled apart at a rate of 50 mm./minute. At the same time, the tearing forces which are characteristic of the strength properties are recorded.
Example ~
A reaction mixture consisting of 97.62% of ethylene, 1.12% of acrylamide, 1.12% of tert-butyl acrylate, and 0.14% of isobutyl vinyl ether and compressed to 1~-900 atm. is continuously fed into the inlet of the reactor described above. The polymerization is effected in the presence of S molar parts of oxygen per million parts of ethylene at a reaction termperature of 249C. After a residence time of 55 seconds of the reaction mixture in the reactor, the copolymer is discharged. An overall 8.1% conversion to polymer is obtained. The polymer con-tains 84.14% of ethylene, 7.7% of acrylamide, 8.0% of tert-butyl acrylate, and 0.16% of isobutyl vinyl ether in copolymerized form.
~ ~5~3~ 3 The melt flow index (MFI 190/2) is 4Ø
The adhesive properties of the product are de-termined by the method described above. The peel strengths are as follows:
Force to initiate peeling 10.0 kgs./cm.
Force to maintain peeling 3.0 kgs./cm.
~.
As described in Example l, a reaction mixture consisting of 98.0% of ethylene, 1.05% of acrylamide, 0.38% of tert-butyl acrylate, and 0.24% of n-butyl vinyl ether is continuously fed into the reactor and compressed to 2,200 atm. The polymerization is effected at 245C. and in the presence of 3 molar parts of oxygen per million parts of ethylene. An overall 8.3% conversion to polymer is obtained. The copolymer consists of 85.4% ethylene, 7.7% of acrylamide, 6.7% of tert-butyl acrylate, and 0.2%~
of n-butyl vinyl ether. The melt flow index of the product is 1.3. The peel strengths are as follows:
Force to initiate peeling 7O4 kgs./cm.
Force to maintain peeling 2.6 kgs./cm.
Example 3 A reaction mixture consisting of 97.6% of ethylene, 0 97% of acrylamide, 0.97% of tert-butyl acrylate, and 0.46% of e~hyl vinyl ether and compressed to 2~250 atm.
is introduced into the reactor at a temperature of 252C
and in the presence of 6 molar parts of oxygen per million ~050363 par~s of ethylene, the residence time of the reaction mixture in the reactor being 56 seconds. A copolymer consisting of 86.2% of ethylene, 7.3% of tert-butyl acrylate, 6.0% of acrylamide, and 0.5% ethyl vinyl ether i~ obtained with an 7.9% overall conversion.
The polymer has a melt flow ind~ (MFI 190/2) of 6.5, a density of 0.926 and a crystalline melting point of 98C. The va-~ues measured for Shore A and D hardness are 87 and 40, respectively.
The peel strengths are as follows:
Force to initiate peeling 13.6 kgs./cm.
Force to maintain peeling 2.9 kgs./cm.
Example 4 A reaction mixture consisting of 97.84% of ethylene, 0.96% of acrylamide, 0.96% of term-amyl acrylate, and 0.24% of n-butyl vinyl ether are introduced into the reactor. Polymerization is ef~ected undar a pressure of 1,900 a~m., in the presence of 3 molar parts of oxygen per million parts of e~hylene are used as an initiator and 1.5 molar parts of propane per 100 parts of ethylene as a polymerization controlling agent. After a residence time of 54 seconds o the reaction mixture in the reactor, a copolymer consisting of 87.4% of ethylene, 5.8% of acryl-amide, 6.6% of ~ert-amyl acrylate, and 0.2% of n-bu~yl vinyl ether is obtained, the conversion to polymer being 8.3%. The melt flow index is 6Ø The peel strengths are as follows:
~()S~)363 Force to initiate peeling 13.1 kgs./cm.
Force to maintain peeling 2.4 kgs./cm.
Example 5 A reaction mixture consisting of 97.7% of ethylene, 0 92% of acrylamide, 0.92% of n-butyl acrylate, and 0.47%
of n-butyl vinyl ether is introduc:ed into the reactor. The polymerization is effected under a pressure of 2,200 atm.
The initiator concentration is 4 molar parts oxygen per million parts of ethylene and the reaction temperature is 242C After a residence time of 53 seconds in the reactor, a copolymer consisting of 86.9% ethylene, 5.6% of acryl-amide, 7.0% of n-butyl acrylate, and 0.5% of n-butyl vinyl ether in copolymerized form is obtained. The overall con-version amounts to 8.9%. The melt flow index is 5.1. The peel strengths are as follows:
Force to initiate peeling 10.0 kgs./cm.
Force to maintain peeling 2.5 kgs./cm.
Example 6 A reaction mixture of 91.3% of ethylene, 1.0%
of methacrylamide, 7.0% of vinyl acetate, and 0.3% of iso-butyl vinyl ether is ed into the polymerization reactor, in the presence o~ 6 molar parts of oxygen per million parts of ethylene as the polymerization initiator, the resulting reaction mixture being continuously discharged.
The pressurP in the reactor is 2,000 atm. and the tempera-ture is 252C After a reaction time of one hour 1150 g of copolymer consisting 85.7% ethylene, 6.9% methacryl-amide, 7.1% of vinyl aceta~e3 and 0.3% of i-butyl vinyl ether in copolymerized form is obt:ained, the conversion being 8.1%. The melt flow index is 43. The peel strengths are as follows:
Force to initiate peeling 8.3 kgs./cm.
Force to maintain peeling 2.1 kgs./cm.
Comparative Example 1 The procedure is as described in Example 1 thrDugh 6, except that the polymerization is effected in the absence of esters of unsaturated carboxylic acid and vinyl ether, a reaction mix~ure of 99.0% of e~hylene and 1% of acryl-amide is polymerized. A copolymer consisting of 91.9% of e~hylene and 8.1% of acrylamide in copolymerized form is obtained, the conversion to polymer being 8.2%. The melt flow index is 0.1. The peel strengths are as follows:
Force to initiate peeling 3.2 kgs,/cm.
Force to maintain peeling 0.5 kgs./cm.
Camparative Example 2 The procedure is as described in Examples 1 - through 6, except that the polymerization is conduc~ed with a reaction mixture of 97.6% of ethylene and 2.4% of n-butyl acrylate. The resultant copolymer consists of 84% of ethylene and 16% of n-butyl acrylate in copoly-merized form. The product has a melt flow index of 1.9 and no adhesion.
3~3 Comparative Example 3 The procedure is as described in Examples 1 through 6, except that ethylene is polymerized with acryl-amide and vinyl isobutyl ether in a 7.8% overall yield.
The resultant ethylene copolymer consists of 92.9% ethylene, 6.1% of acrylamide, and 1.0% of vinyl isobutyl ether in copolymerized form. The melt flow index is 1Ø The peel strengths are as follows:
Force to initiate peeling 3.8 kgs./cm.
Force to maintain peeling O.S kgs./cm.
Comparative Examples 4 throu~h 9 The polymerizations are effected by the procedure described in Examples 1 through 6. The comonomer concentra-tions in the starting reaction mixtures are selected so that the resultant copolymers consist of 79 to 85% ethylene, 6 to 8% of acrylamide and 8.6, 9.0, 9.7, 11.1 and 13.6% of n-butyl acrylate or tert-butyl acrylate. The melt flow index values are 0.9, 0.7, 0.3, 9.8, 3.5, 4.4, respectively.
The measured pee-l strengths are ~hown in Table 1. It is clear that terpolymers having an acrylamide content in the range from 6 to 8% give optimum peeling strengths if the copolymer cantains approximately 9 to 12% of acrylic acid ester. If 0.1 to 0.5% by weight of alkyl vinyl ether is incorporated into the polymer, only 7 to 8% of acrylic acid ester is necessary to achieve the same peel strength.
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German published Patent Application DAS 1,645,018 describes the copolymerization of ethylene with tert-butylamino ethyl methacrylate or an ester of an unsatura-ted carboxylic acid, and the amide of an unsaturated carboxylic acid to produce copolymers useful for the pro-duction of hollow-shaped articles and film. These articles can be produced by the usual methods, such as casting, ex-trusion and injection molding.
. -2-:1~50363 German published Patent Application DAS 1,645,024 relates to a process for producing ethylene copolymers con-taining from 1-10 mole percent of a vinyl ether, from 0.5-20 mole percent o~ unsubstituted acryl or methacrylamides and 70-98.5 mole percent of ethylene.
German Patent Application P 24 00 978.7 of the present inventors, which has not yet been published, teaches a process for bonding together or coating materials using as an adhesive or coating composition, an olefin copolymer.
This copolymPr contains 70-90 parts of ethylene, ~.5-10 parts of the amide of an e~hy~enically unsaturated carboxylic acid and 0.5-20 parts of the ester of an ethylenically un-saturated carboxylic acid. When producing polymers having the~oomposition mentioned above,it is necessary, to achieve commercially useful melt flow indices, to maintain high modifier concentrations. For example, the polymerization is ef~ected in the presence of 10-12 percent of propane as a modifying ingredient. This percentage is based on the weight of ethylene. This substantial dilution of the ethylene results in a marked reduction in conversion. Such high concentrations of modifier are not necessary in the process according to the present invention because the vinyl ether has a molecular weight-controlling action. In addition, the adhesive properties of these polymers are largely dependent upon their composition. Maximum adhesive strength is achieved only within a very narrow concentration ~ 50363 range of the comonomers. Therefore, it is necessary when producing the polymer that the individual components are maintained in the precise proportion requi.red.
The prior art also shows the use of binary and tertiary ethylene copolymers containing acrylic acid for bonding and coating various materials and substrates.
These high molecular weight compounds also exhibit inherent deficiencies which are due to the presence of carboxyl groups in the macromolecule. Because of the formation of hydrogen bridges, the carboxyl groups favor the accumu-lation of water between the coating and the substrate.
This results in delamination and detachment of the polymer from the substrate. This phenomenon is particularly serious in cases in which the bonding m~çhanism is based on the carbo~lic acid groups of the adhesion promoter; for example, when the copolymers adhere to metals.
It has now been found that the deficiencies and disadvantages mentioned above are not exhibited by the quat-ernary copolymers o~ the present invention. These copolymers consis~ of 70-90 parts of ethylene, 0.5-15 parts of an alkyl ester (wherein the alkyl group contains up to 8 carbon atoms) of an unsaturated monocarboxylic acid having 3-6 carbon atoms or the vinyl ester of a saturated monocarboxylic acid having up to 3 carbon atoms, 0.5-10 parts of an amide of an unsaturated monocarboxylic acid having 3-6 carbon atoms, and 0.1-5 parts of a vinyl ether having up to 10 carbon atoms; the sum of the parts totalling 100 ~LOS~363 It is a preferred embodlment of this invention that the quaternary copolymers contain 80-90 parts of ethy-lene, 7-12 parts of an alkyl ester (wherein the alkyl group contains up to 8 carbon!atoms) oE an unsaturated monocarboxy-lic acid or a vinyl es~er of a sa~urated monocarboxylic acid having up to 3 carbon atoms, 5-8 parts of an amide of an unsaturated carboxylic acid having 3-6 carbon atoms and 0.1-1 part of an aliphatic or aromatic vinyl ether having up to 10 carbon atoms; the sum of the parts totalling 100.-The above-mentioned quaternary copolymers are characterized by crystalline melting points of 95C.-100C.
and densities of 0.925-0.938, measured acco~ding to DIN 53 479.
Products having melt flow index values of 0.1-100, especially those having melt flow index values between 1 and 50 are suitable as adhesives. As compared with terpolymers of ethylene, acrylic acid and acrylic acid esters, the quater-nary copolymers have a higher modulus of elasticity.
Examples of esters of unsaturated carboxylic acids which may be used as comonomers include ethyl acrylate, n-propyl acrylate, n-butyl acrylate, tert-butyl acrylate, t~rt-butyl methacrylate, tert-butyl crotonate, and 2-ethyl hexyl acrylate. Particularly suitable are the es~ers of acrylic and methacrylic acids with tert-butanol and tert-amyl alcohol. Vinyl acetate is representative of the vinyl esters of saturated carboxylic acids.
For the purposes of this invention, acrylamide, methacrylamide and crotonic acid amide are the preferred i~5~363 amides of unsaturated carboxylic a~ids.
Examples of copolymerizable ethers include methyl ~inyl ether, ethyl vinyl ether, propyl vinyl ether, i-butyl vinyl etherS and n-butyl vinyl ether. The type of the ether used does not affect the adhesiveness of the copolymer.
The copolymers according to the present invention are produced at pressures of 400 to 4,000 bars and ~empera-tures of 100C. to 350C. The polymerization is carried out in the presence of catalytic quantiti~s of free radical initiators (e.g. oxygen, in amounts of 2 to 250 molar parts per million parts of ethylene). Furthermore, peroxides and other free radical forming substances, such as tert-butyl perbenzoate, dilauryl peroxide, didecanoyl peroxide, di-tert-butyl peroxide, azoisobutyrodinitrile may be used alone or in mixture in amounts of 2 to 200 molar parts per million parts of ethylene. The polymerization may be effec~ed in the presence of modifying ingredients such as aliphatic alcohols, aliphatic saturated carbonyl compounds, chlorinated hydrocarbons and hydrogen. The process according to this invention may be effected either continuously or batch-wise; the continuous operation is preferred. When operating continuously, the copolymer is withdrawn ~r~m the reactor.
The unreacted portion of the monomers, the initiator and the modifying ingredients are then recycled.
The quaternary copolymers prepared according to the present invention, which contain 0.1 to 1.0% of an alkyl ~(~5~336~
vinyl ether, exhibit excellent adhesive strength on various substrates such as metals and woods. This adhesive strength is maintained at a high level regardless of the ratio of the other comonomers.
The copolymers strongly adhere to the substrate as coatings, impregnations and surface layers, especially if applied in the molten state. The copolymers may be used in this manner as thermal plastic adhesives for metalsg ceramic materials, paper, textiles, wood, glass, leather and plastic materials.
~ue to the presence of hydrophilic amide groups, ~he quaternary polymers may also be processed to produce stable emulsions which permit the use of the polymers in ~inely divided form. When used in the form of emulsions and solutions of the copolymers, it is possible to produce very thin films on metals, ceramic materials, glass, tex-~iles, wood, paper, leather, and plastic materials These films are useful as adhesives for lamination with polyole-fins such as polyethylene or rubber.
A surprising result of the present invention is that a smaller amount of an alkyl ester of an unsaturated carboxylic acid is needed than that which would be ex-pected to obtain satisfactory adhesive strength. This result is shown even when the copolymer contains only a small amount of an alkyl ether.
~1~50363 The polymers or the materials that are impreg-nated with the polymers can be printed. Their affinity with dyes is remarkable. In addition, the copolymers are useful as additives in coating compositions, especially those polymers which con~ain a relatively high proportion of copolymerized comonomers.
The following examples illustrate the production of the new polymers and their use for bonding or coating substrates and materials In these examples, parts and percentages are by weight unless otherwis~ stated.
A. Production of the polymers The quaternary copolymers are produced in a con-tinuously operated laboratory autoclave unit, comprising an autoclave equipped with a magnetic stirrer and an electrical heater. Before it is introduced into the auto-clave, the ethylene is mixed with gaseous additives such as oxygen as an initiator and, if necessary or desired, propane as a modifier. The mixture is then compressed to the reaction pressure. The reaction mixture is then passed through a preheater and into the autoclave. At ~he same time, the comonomers, if necessary, are dissolved or diluted and are then fed into the reactor by means o two high pressure metering pumps having different delîveries. Low molecular weight polar organic compounds such as methanol, ethanol and butanol have been found ~ ~S~ 3 ~ 3 to be particularly useful solvents. The polymerization is effected at temperatures between 170C. and 280C.
The~polymer-monomer mixture leaving the reactor is de-pressurized to about 2 to 3 bars by means of a cont~ol valve. In doing so, the polymer formed is separated and collected in alternately filled receivers.
B. Determination of adhesive strength Cleaned aluminum strips o 100 mm. in length, 100 mm. in width and 1.5 mm. in thickness were bonded to-gether by pressing (pressure, 3 kgs./sq.cm.; pressing time, 30 to 40 seconds; compression temperature 180C.) over a length of 70 mm. by means of films consisting of the particular ethylene copolymers and produced by compression or e~trusion through a slot die. In another experiment9 aluminum strips having the same dimensions were bonded under the same conditions to a sheet of high pressure poly-ethylene of 4 mm. thickness. The unbonded lengths of the aluminum strips were bent at right angles in opposite dire~tions.
The adhesive properties are primarily demonstrated by the peel strength. This value represents the force per tear length which is necessary to braak the bond. With respect to the adhesive property, it is necessary to dif-ferentiate between the force required to initiate peeling and the force required to maintain peeling per tear length.
~ OS0363 The force to maintain peeling is important in determining the adhesive strength of ~he product being tested.
The physical data mentioned above is de~ermined by means of a tensile tester. Metal sheets (30 mm. by 100 mm.) are bent at an angle and are placed in the grippers of the testing machine in such a manner th~t the adhesive coated surface (70 mm. by 100 mm.) extends at right angles with respect to grippers. The system is pulled apart at a rate of 50 mm./minute. At the same time, the tearing forces which are characteristic of the strength properties are recorded.
Example ~
A reaction mixture consisting of 97.62% of ethylene, 1.12% of acrylamide, 1.12% of tert-butyl acrylate, and 0.14% of isobutyl vinyl ether and compressed to 1~-900 atm. is continuously fed into the inlet of the reactor described above. The polymerization is effected in the presence of S molar parts of oxygen per million parts of ethylene at a reaction termperature of 249C. After a residence time of 55 seconds of the reaction mixture in the reactor, the copolymer is discharged. An overall 8.1% conversion to polymer is obtained. The polymer con-tains 84.14% of ethylene, 7.7% of acrylamide, 8.0% of tert-butyl acrylate, and 0.16% of isobutyl vinyl ether in copolymerized form.
~ ~5~3~ 3 The melt flow index (MFI 190/2) is 4Ø
The adhesive properties of the product are de-termined by the method described above. The peel strengths are as follows:
Force to initiate peeling 10.0 kgs./cm.
Force to maintain peeling 3.0 kgs./cm.
~.
As described in Example l, a reaction mixture consisting of 98.0% of ethylene, 1.05% of acrylamide, 0.38% of tert-butyl acrylate, and 0.24% of n-butyl vinyl ether is continuously fed into the reactor and compressed to 2,200 atm. The polymerization is effected at 245C. and in the presence of 3 molar parts of oxygen per million parts of ethylene. An overall 8.3% conversion to polymer is obtained. The copolymer consists of 85.4% ethylene, 7.7% of acrylamide, 6.7% of tert-butyl acrylate, and 0.2%~
of n-butyl vinyl ether. The melt flow index of the product is 1.3. The peel strengths are as follows:
Force to initiate peeling 7O4 kgs./cm.
Force to maintain peeling 2.6 kgs./cm.
Example 3 A reaction mixture consisting of 97.6% of ethylene, 0 97% of acrylamide, 0.97% of tert-butyl acrylate, and 0.46% of e~hyl vinyl ether and compressed to 2~250 atm.
is introduced into the reactor at a temperature of 252C
and in the presence of 6 molar parts of oxygen per million ~050363 par~s of ethylene, the residence time of the reaction mixture in the reactor being 56 seconds. A copolymer consisting of 86.2% of ethylene, 7.3% of tert-butyl acrylate, 6.0% of acrylamide, and 0.5% ethyl vinyl ether i~ obtained with an 7.9% overall conversion.
The polymer has a melt flow ind~ (MFI 190/2) of 6.5, a density of 0.926 and a crystalline melting point of 98C. The va-~ues measured for Shore A and D hardness are 87 and 40, respectively.
The peel strengths are as follows:
Force to initiate peeling 13.6 kgs./cm.
Force to maintain peeling 2.9 kgs./cm.
Example 4 A reaction mixture consisting of 97.84% of ethylene, 0.96% of acrylamide, 0.96% of term-amyl acrylate, and 0.24% of n-butyl vinyl ether are introduced into the reactor. Polymerization is ef~ected undar a pressure of 1,900 a~m., in the presence of 3 molar parts of oxygen per million parts of e~hylene are used as an initiator and 1.5 molar parts of propane per 100 parts of ethylene as a polymerization controlling agent. After a residence time of 54 seconds o the reaction mixture in the reactor, a copolymer consisting of 87.4% of ethylene, 5.8% of acryl-amide, 6.6% of ~ert-amyl acrylate, and 0.2% of n-bu~yl vinyl ether is obtained, the conversion to polymer being 8.3%. The melt flow index is 6Ø The peel strengths are as follows:
~()S~)363 Force to initiate peeling 13.1 kgs./cm.
Force to maintain peeling 2.4 kgs./cm.
Example 5 A reaction mixture consisting of 97.7% of ethylene, 0 92% of acrylamide, 0.92% of n-butyl acrylate, and 0.47%
of n-butyl vinyl ether is introduc:ed into the reactor. The polymerization is effected under a pressure of 2,200 atm.
The initiator concentration is 4 molar parts oxygen per million parts of ethylene and the reaction temperature is 242C After a residence time of 53 seconds in the reactor, a copolymer consisting of 86.9% ethylene, 5.6% of acryl-amide, 7.0% of n-butyl acrylate, and 0.5% of n-butyl vinyl ether in copolymerized form is obtained. The overall con-version amounts to 8.9%. The melt flow index is 5.1. The peel strengths are as follows:
Force to initiate peeling 10.0 kgs./cm.
Force to maintain peeling 2.5 kgs./cm.
Example 6 A reaction mixture of 91.3% of ethylene, 1.0%
of methacrylamide, 7.0% of vinyl acetate, and 0.3% of iso-butyl vinyl ether is ed into the polymerization reactor, in the presence o~ 6 molar parts of oxygen per million parts of ethylene as the polymerization initiator, the resulting reaction mixture being continuously discharged.
The pressurP in the reactor is 2,000 atm. and the tempera-ture is 252C After a reaction time of one hour 1150 g of copolymer consisting 85.7% ethylene, 6.9% methacryl-amide, 7.1% of vinyl aceta~e3 and 0.3% of i-butyl vinyl ether in copolymerized form is obt:ained, the conversion being 8.1%. The melt flow index is 43. The peel strengths are as follows:
Force to initiate peeling 8.3 kgs./cm.
Force to maintain peeling 2.1 kgs./cm.
Comparative Example 1 The procedure is as described in Example 1 thrDugh 6, except that the polymerization is effected in the absence of esters of unsaturated carboxylic acid and vinyl ether, a reaction mix~ure of 99.0% of e~hylene and 1% of acryl-amide is polymerized. A copolymer consisting of 91.9% of e~hylene and 8.1% of acrylamide in copolymerized form is obtained, the conversion to polymer being 8.2%. The melt flow index is 0.1. The peel strengths are as follows:
Force to initiate peeling 3.2 kgs,/cm.
Force to maintain peeling 0.5 kgs./cm.
Camparative Example 2 The procedure is as described in Examples 1 - through 6, except that the polymerization is conduc~ed with a reaction mixture of 97.6% of ethylene and 2.4% of n-butyl acrylate. The resultant copolymer consists of 84% of ethylene and 16% of n-butyl acrylate in copoly-merized form. The product has a melt flow index of 1.9 and no adhesion.
3~3 Comparative Example 3 The procedure is as described in Examples 1 through 6, except that ethylene is polymerized with acryl-amide and vinyl isobutyl ether in a 7.8% overall yield.
The resultant ethylene copolymer consists of 92.9% ethylene, 6.1% of acrylamide, and 1.0% of vinyl isobutyl ether in copolymerized form. The melt flow index is 1Ø The peel strengths are as follows:
Force to initiate peeling 3.8 kgs./cm.
Force to maintain peeling O.S kgs./cm.
Comparative Examples 4 throu~h 9 The polymerizations are effected by the procedure described in Examples 1 through 6. The comonomer concentra-tions in the starting reaction mixtures are selected so that the resultant copolymers consist of 79 to 85% ethylene, 6 to 8% of acrylamide and 8.6, 9.0, 9.7, 11.1 and 13.6% of n-butyl acrylate or tert-butyl acrylate. The melt flow index values are 0.9, 0.7, 0.3, 9.8, 3.5, 4.4, respectively.
The measured pee-l strengths are ~hown in Table 1. It is clear that terpolymers having an acrylamide content in the range from 6 to 8% give optimum peeling strengths if the copolymer cantains approximately 9 to 12% of acrylic acid ester. If 0.1 to 0.5% by weight of alkyl vinyl ether is incorporated into the polymer, only 7 to 8% of acrylic acid ester is necessary to achieve the same peel strength.
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Claims (14)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method of coating a material comprising apply-ing a copolymer consisting essentially of a) a first comonomer comprising 70-90 parts by weight of ethylene per 100 parts by weight of said copolymer, b) a second comonomer present in an amount of 0.5 to 15 parts by weight per 100 parts by weight of said copolymer, said second comonomer being selected from:
1) an alkyl ester wherein the alkyl group contains up to 8 carbon atoms, of an unsaturated monocarboxylic acid having 3 to 6 carbon atoms, or 2) a vinyl ester of a saturated carboxylic acid having up to 3 carbon atoms, c) a third comonomer comprising an amount of an amide of an unsaturated monocarboxylic acid having 3 to 6 carbon atoms, said amount being 0.5 to 10 parts by weight per 100 parts by weight of said copolymer and, d) a forth comonomer comprising an amount of a vinyl ether having up to 10 carbon atoms, said amount being 0.1 to 5 parts by weight per 100 parts by weight of said copolymer, to a first material to form a coated material.
1) an alkyl ester wherein the alkyl group contains up to 8 carbon atoms, of an unsaturated monocarboxylic acid having 3 to 6 carbon atoms, or 2) a vinyl ester of a saturated carboxylic acid having up to 3 carbon atoms, c) a third comonomer comprising an amount of an amide of an unsaturated monocarboxylic acid having 3 to 6 carbon atoms, said amount being 0.5 to 10 parts by weight per 100 parts by weight of said copolymer and, d) a forth comonomer comprising an amount of a vinyl ether having up to 10 carbon atoms, said amount being 0.1 to 5 parts by weight per 100 parts by weight of said copolymer, to a first material to form a coated material.
2. The method of claim 1 wherein said coated material is affixed to a second material whereby said coated material is bonded to said second material.
3. The method of claim 1 wherein said first comonomer is present in an amount of 80 to 90 parts by weight per 100 parts by weight of said copolymer.
4. The method of claim 1 wherein said second comonomer is present in an amount of 7 to 12 parts by weight per 100 parts by weight of said copolymer.
5. The method of claim 1 wherein said third comonomer is present in an amount of 5 to 8 parts by weight per 100 parts by weight of said copolymer.
6. The method of claim 1 wherein said fourth comonomer is present in an amount of 0.1 to 1 part by weight per 100 parts by weight of said copolymer.
7. The method of claim 1 wherein a) said first comonomer is present in an amount of 80 to 90 parts by weight per 100 parts by weight of said copolymer, b) said second comonomer is present in an amount of 7 to 12 parts by weight per 100 parts by weight of said copolymer.
c) said third comonomer is present in an amount of 5 to 8 parts by weight per 100 parts by weight of said copolymer, and d) said fourth comonomer is present in an amount of 0.1 to 1 part by weight per 100 parts by weight of said copolymer.
c) said third comonomer is present in an amount of 5 to 8 parts by weight per 100 parts by weight of said copolymer, and d) said fourth comonomer is present in an amount of 0.1 to 1 part by weight per 100 parts by weight of said copolymer.
8. The method of claim 1 wherein second second comonomer is selected from the group consisting of tert-butyl acrylate, tert-butyl methacrylate, tert-amyl acrylate, and tert-amyl methacrylate.
9. The method of claim 1 wherein said second comonomer is vinyl acetate.
10. The method of claim 1 wherein said third comonomer is selected from the group consisting of acrylamide, methacrylamide, and crotonic acid amide.
11. The method of claim 1 wherein said fourth comonomer is selected from the group consisting of methyl vinyl ether, propyl vinyl ether, i-butyl vinyl ether, and n-butyl vinyl ether.
12. The method of claim 1 having a melt flow index of 0.1 to 100.
13. The method of claim 1 wherein said melt flow index is 0.1 to 50.
14. The method of claim 1 wherein said materials are selected from the group consisting of metals, ceramics, paper, textiles, wood, glass, leather, and plastics.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2448342A DE2448342C3 (en) | 1974-10-10 | 1974-10-10 | Process for the production of copolymers of ethylene and their use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1050363A true CA1050363A (en) | 1979-03-13 |
Family
ID=5928005
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA237,321A Expired CA1050363A (en) | 1974-10-10 | 1975-10-09 | Copolymers of ethylene process for producing them and their use |
Country Status (15)
| Country | Link |
|---|---|
| JP (2) | JPS51125176A (en) |
| AT (1) | AT335584B (en) |
| BE (1) | BE834240A (en) |
| CA (1) | CA1050363A (en) |
| DE (1) | DE2448342C3 (en) |
| DK (1) | DK145719C (en) |
| ES (1) | ES441497A1 (en) |
| FR (1) | FR2287457A1 (en) |
| GB (1) | GB1480565A (en) |
| IT (1) | IT1056145B (en) |
| NL (1) | NL158513B (en) |
| RO (1) | RO66795A (en) |
| SE (1) | SE424329B (en) |
| SU (1) | SU593673A3 (en) |
| ZA (1) | ZA756294B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54114889U (en) * | 1978-01-31 | 1979-08-11 | ||
| JPS59142130A (en) * | 1983-02-03 | 1984-08-15 | 湊紙器株式会社 | Method of processing carton material |
| JPS6178620U (en) * | 1984-10-30 | 1986-05-26 | ||
| JPS61106230A (en) * | 1984-10-30 | 1986-05-24 | 積水化成品工業株式会社 | Size changing device for mold for molding set-up box |
| JPS6178621U (en) * | 1984-10-30 | 1986-05-26 | ||
| JPH0357466Y2 (en) * | 1985-09-20 | 1991-12-27 | ||
| JPS6253133U (en) * | 1985-09-20 | 1987-04-02 | ||
| JPS6268734A (en) * | 1985-09-20 | 1987-03-28 | 積水化成品工業株式会社 | Box making device |
| DE10343901A1 (en) * | 2003-09-19 | 2005-04-14 | Basf Ag | Amide group-containing ethylene terpolymers and their use |
| EP3181599A1 (en) * | 2015-12-18 | 2017-06-21 | Borealis AG | Novel process for producing a polar ethylene copolymer with low melt flow rate |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL126214C (en) * | 1961-06-21 | 1900-01-01 | ||
| FR1471882A (en) * | 1963-09-18 | 1967-03-03 | Permutit Co Ltd | Film forming terpolymer |
| US3405200A (en) * | 1965-07-08 | 1968-10-08 | Toyo Boseki | Polyolefin composition containing a copolymer of ethylene-acrylamide-ethylenically unsaturated compound |
| DE1645018A1 (en) * | 1965-08-02 | 1970-05-14 | Monsanto Co | Copolymers and processes for making the same |
| US3451982A (en) * | 1965-08-04 | 1969-06-24 | Monsanto Co | Terpolymers of ethylene,a vinyl ester and an unsaturated amide |
| US3458487A (en) * | 1965-08-12 | 1969-07-29 | Monsanto Co | Interpolymers of ethylene,an unsaturated amide,and a vinyl ether |
| DE1569907A1 (en) * | 1966-01-19 | 1969-08-14 | Basf Ag | Process for bonding molded structures made of polyolefins |
| DE1669638B2 (en) * | 1966-03-08 | 1972-09-07 | Badische Anilin & Soda Fabrik AG, 6700 Ludwigshafen | MOLDING COMPOUNDS BASED ON BITUMEN, ETHYLENE MIXED POLYMERIZES AND POLYISOBUTYLENE |
| DE1745001B2 (en) * | 1967-10-12 | 1979-07-12 | Imhico Ag, Zuerich (Schweiz) | Copolymers of ethylene suitable for film production and processes for their production |
-
1974
- 1974-10-10 DE DE2448342A patent/DE2448342C3/en not_active Expired
- 1974-10-29 AT AT867774A patent/AT335584B/en not_active IP Right Cessation
-
1975
- 1975-09-26 NL NL7511390.A patent/NL158513B/en not_active IP Right Cessation
- 1975-10-01 FR FR7530100A patent/FR2287457A1/en active Granted
- 1975-10-01 SU SU752176641A patent/SU593673A3/en active
- 1975-10-02 SE SE7511065A patent/SE424329B/en unknown
- 1975-10-02 RO RO7583506A patent/RO66795A/en unknown
- 1975-10-03 GB GB40626/75A patent/GB1480565A/en not_active Expired
- 1975-10-03 ZA ZA00756294A patent/ZA756294B/en unknown
- 1975-10-03 ES ES441497A patent/ES441497A1/en not_active Expired
- 1975-10-03 JP JP50119675A patent/JPS51125176A/en active Granted
- 1975-10-03 DK DK447975A patent/DK145719C/en not_active IP Right Cessation
- 1975-10-06 BE BE160732A patent/BE834240A/en unknown
- 1975-10-09 IT IT51723/75A patent/IT1056145B/en active
- 1975-10-09 CA CA237,321A patent/CA1050363A/en not_active Expired
-
1977
- 1977-07-13 JP JP8401577A patent/JPS5388835A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| SU593673A3 (en) | 1978-02-15 |
| JPS5388835A (en) | 1978-08-04 |
| DE2448342A1 (en) | 1976-04-22 |
| DE2448342C3 (en) | 1984-05-30 |
| ES441497A1 (en) | 1977-04-01 |
| AT335584B (en) | 1977-03-25 |
| JPS51125176A (en) | 1976-11-01 |
| FR2287457A1 (en) | 1976-05-07 |
| JPS5646504B2 (en) | 1981-11-04 |
| RO66795A (en) | 1980-03-15 |
| FR2287457B1 (en) | 1980-05-30 |
| NL7511390A (en) | 1976-04-13 |
| ATA867774A (en) | 1976-07-15 |
| SE7511065L (en) | 1976-04-12 |
| DK145719C (en) | 1983-07-25 |
| DK145719B (en) | 1983-02-07 |
| BE834240A (en) | 1976-04-06 |
| DK447975A (en) | 1976-04-11 |
| SE424329B (en) | 1982-07-12 |
| JPS5249027B2 (en) | 1977-12-14 |
| IT1056145B (en) | 1982-01-30 |
| ZA756294B (en) | 1976-09-29 |
| NL158513B (en) | 1978-11-15 |
| GB1480565A (en) | 1977-07-20 |
| DE2448342B2 (en) | 1980-02-07 |
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