CA1062400A - Poly(higher-1-olefin-co-propylene) copolymers as hot-melt, pressure-sensitive adhesives - Google Patents
Poly(higher-1-olefin-co-propylene) copolymers as hot-melt, pressure-sensitive adhesivesInfo
- Publication number
- CA1062400A CA1062400A CA247,772A CA247772A CA1062400A CA 1062400 A CA1062400 A CA 1062400A CA 247772 A CA247772 A CA 247772A CA 1062400 A CA1062400 A CA 1062400A
- Authority
- CA
- Canada
- Prior art keywords
- copolymer
- propylene
- olefin
- sensitive adhesive
- hexene
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
-
- 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
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- 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
- C08F210/14—Monomers containing five or more carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
Abstract
\
ABSTRACT OF THE DISCLOSURE
This invention relates to single component, hot-melt, pressure-sensitive adhesives based on propylene and/or 1-butene/
higher 1-olefin copolymers containing 40-60 mole % of the higher 1-olefin. Suitable comonomers include 1-hexene through 1-decene.
These new adhesives can be readily applied to substrates such as tape by means of conventional hot-melt coating equipment and thereby eliminate the solvent pollution problems associated with the application of current solvent-based pressure-sensitive adhesives. Our hot-melt coated tapes generally have pressure-sensitive adhesive properties at least equivalent to those of solvent coated pressure-sensitive tapes.
ABSTRACT OF THE DISCLOSURE
This invention relates to single component, hot-melt, pressure-sensitive adhesives based on propylene and/or 1-butene/
higher 1-olefin copolymers containing 40-60 mole % of the higher 1-olefin. Suitable comonomers include 1-hexene through 1-decene.
These new adhesives can be readily applied to substrates such as tape by means of conventional hot-melt coating equipment and thereby eliminate the solvent pollution problems associated with the application of current solvent-based pressure-sensitive adhesives. Our hot-melt coated tapes generally have pressure-sensitive adhesive properties at least equivalent to those of solvent coated pressure-sensitive tapes.
Description
; ~
~06Z~Q0 This invention relates to propylene containing copolymers which contain 40 to 60 mole percent of linear 1-- olefins having from 6-10 carbon atoms. These copolymers are ; permanently tacky and are useful as single component hot-melt, -pressure-sensitive adhesives.
Pressure-sensitive adhesive (PSA) products have experienced a rapid growth rate in recent years because of their ease of application. Typical pressure-sensitive adhesive -~
applications include/ for example, tapes ~consumer, industrial, and surgical)~ labels, decals, films, floor tile and wall and -shelf coverings. Until recently, virtually all pressure-sensitive compositions were based on blends of high molecular weight synthetic and natural rubbers with tackifiers. Fre-quently fillers such as zinc oxide or magnesium oxide are used ; in PSA formulations which are applied to opaque backing sub-strates. Typical backing materials include paper, cellophane, plasticized poly(vinyl chloride), polyester film, cellulose acetate film, cloth, foamed polymers (e.g., foamed polystyrene ! or poLypropylene), metal foils, felt, cork and the like. Al-though PSA compositions have generally been applied to the backings from solvents, there is a strong desire to switch to PSA materials which can be applied as hot melts to eliminate solvent pollution during manufacturing of the products. Also, a non-solvent adhesive is desirable since many solvents are in short supply.
Heretofore it has been recognized that certain prior art copolymers containing l-hexene or l-octene were permanently tacky. However, it was not until recently that the critical property requirements for a pressure-sensitive adhesive material were known. Therefore, not all copolymers which are permanently tacky are useful as pressure-sensitive adhesives.
For example, poly-l-hexene or l-hexene copolymers containing ,~4~
~ .
minor amounts of propylene (e.g., 5-20 wt. ~ propylene) are permanently tacky but they have very poor cohesive strength.
Therefore, such materials leave a residue when coated poly-`~ ester tapes are stripped away from steel plates and they fail in the static shear test after less than 100 min. (~1000 min. -;~ required to pass static shear test).
... .
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.' ~' ``` ~062401D
The copolymers described in Canadian Patent 856,337 are made with highly stereospecific catalysts and even those containing equal molar amounts of propylene and l-hexene contained substantial ;~ blocks of each monomer. This "blockiness" prevents these copolymers :,, .
from retaining a high degree of tack. Therefore, the adhesives basically are hot melt adhesives which require reactivated at elevated temperatures (e.g., 1~0F.) for bonding various substrates but are not pressure-sensitive adhesives as defined in the present inventlon.
, :
~`~ Also, crystalline copolymers based on l-butene, or propylene, -~ 10 with other straight chain olefins having at least three carbon atoms, ;~ as described in French Patent 1,~396,954 to Guillet et al issued March 8, 1965, having melting points of 80-125C., densities of :,......................................................................... :. . ~
~ 0.86-0.93, molecular weights of 3,000-8,000, and penetration hardness ~ . . .
~ values of <4 (250 g. weight). While French patent 1,396,054 teaches , `` that these crystalline copolymers can be used as thermoplastic or hot melt adhesives, these crystalline copolymers are not suitable as . , .
pressure-sensitive adhesives. United States Patent No. 3,635,755 to Ballath et al issued January 18, 1972 teaches that certain olefin-copolymers having intrinsic viscosities of 1.5-7.0 and a molecular ., structure such that 40-75% by weight of the polymer is isotactic ~ material are useful as pressure-sensitive adhesives. The polymers ~ ;
.!1 are made at 30C. using a R3Al/TiC14 catalyst. Monomers used include olefins having 2 to 16 carbon atoms. These high molecular weight polymers are applied to the backing material (silicone-coated kraf~
i paper) from heptane solutions containing 16 wt. % polymer. Only qualitative tests (such as touching the adhesive with a finger) are ~, .. . .
~ used to determine if the materials have pressure-sensitive properties.
;~~ It is apparent, therefore, that it would be an advance in the state of the art to prdvide a group of selected propylene copolymers 30 which are permanently tacky and meet the property requirements for a `
hot-melt, pressure-sensitive adhesive. `-''~
.-., ,~ ` ' ' ~ .
~ - 2 - ~
. .
10~;~400 Accordingly by the present invention there is provided a hot melt, pressure sensitive adhesive comprising an amorphous copolymer of at least one lower l-olefin selected from the group consisting of propylene and l-butene and at least one higher l-olefin selected from the group consisting of l-hexene, l-heptene, l-octene, l-nonene and l-decene, said copolymer containing 40 to 60 mole percent higher I-olefin and having a melt viscosity at 190C within the range of lO,000 cp. to ; 75,000 cp., a density within the range of 0.85 to 0.86, a glass transition temperature within the range of -30C to -45C, and having no melting point measurable b~ Differential Scanning Calorimetry.
In order to meet the critical requirements for use as a general purpose, pressure-sensitive adhesive, a material must:
~, l. Provide a peel strength of at least 2.5 lb./in -Pressure Sensitive Tape Council (PSTC) Test -l, "Peel Adhesion for Single Coated Tape, 180 Angle".
~06Z~Q0 This invention relates to propylene containing copolymers which contain 40 to 60 mole percent of linear 1-- olefins having from 6-10 carbon atoms. These copolymers are ; permanently tacky and are useful as single component hot-melt, -pressure-sensitive adhesives.
Pressure-sensitive adhesive (PSA) products have experienced a rapid growth rate in recent years because of their ease of application. Typical pressure-sensitive adhesive -~
applications include/ for example, tapes ~consumer, industrial, and surgical)~ labels, decals, films, floor tile and wall and -shelf coverings. Until recently, virtually all pressure-sensitive compositions were based on blends of high molecular weight synthetic and natural rubbers with tackifiers. Fre-quently fillers such as zinc oxide or magnesium oxide are used ; in PSA formulations which are applied to opaque backing sub-strates. Typical backing materials include paper, cellophane, plasticized poly(vinyl chloride), polyester film, cellulose acetate film, cloth, foamed polymers (e.g., foamed polystyrene ! or poLypropylene), metal foils, felt, cork and the like. Al-though PSA compositions have generally been applied to the backings from solvents, there is a strong desire to switch to PSA materials which can be applied as hot melts to eliminate solvent pollution during manufacturing of the products. Also, a non-solvent adhesive is desirable since many solvents are in short supply.
Heretofore it has been recognized that certain prior art copolymers containing l-hexene or l-octene were permanently tacky. However, it was not until recently that the critical property requirements for a pressure-sensitive adhesive material were known. Therefore, not all copolymers which are permanently tacky are useful as pressure-sensitive adhesives.
For example, poly-l-hexene or l-hexene copolymers containing ,~4~
~ .
minor amounts of propylene (e.g., 5-20 wt. ~ propylene) are permanently tacky but they have very poor cohesive strength.
Therefore, such materials leave a residue when coated poly-`~ ester tapes are stripped away from steel plates and they fail in the static shear test after less than 100 min. (~1000 min. -;~ required to pass static shear test).
... .
':,', ' ' .
. 10 ~. -~ ~ .
~ , .
.',J
. _ " ' .
,' I .
',..
'' .
,,~~ ' .
`,:, .
.
, ,.
... ..
"
., . .
, ..
;i~ 30 . . .
, . .
,, - la -r, A
.' ~' ``` ~062401D
The copolymers described in Canadian Patent 856,337 are made with highly stereospecific catalysts and even those containing equal molar amounts of propylene and l-hexene contained substantial ;~ blocks of each monomer. This "blockiness" prevents these copolymers :,, .
from retaining a high degree of tack. Therefore, the adhesives basically are hot melt adhesives which require reactivated at elevated temperatures (e.g., 1~0F.) for bonding various substrates but are not pressure-sensitive adhesives as defined in the present inventlon.
, :
~`~ Also, crystalline copolymers based on l-butene, or propylene, -~ 10 with other straight chain olefins having at least three carbon atoms, ;~ as described in French Patent 1,~396,954 to Guillet et al issued March 8, 1965, having melting points of 80-125C., densities of :,......................................................................... :. . ~
~ 0.86-0.93, molecular weights of 3,000-8,000, and penetration hardness ~ . . .
~ values of <4 (250 g. weight). While French patent 1,396,054 teaches , `` that these crystalline copolymers can be used as thermoplastic or hot melt adhesives, these crystalline copolymers are not suitable as . , .
pressure-sensitive adhesives. United States Patent No. 3,635,755 to Ballath et al issued January 18, 1972 teaches that certain olefin-copolymers having intrinsic viscosities of 1.5-7.0 and a molecular ., structure such that 40-75% by weight of the polymer is isotactic ~ material are useful as pressure-sensitive adhesives. The polymers ~ ;
.!1 are made at 30C. using a R3Al/TiC14 catalyst. Monomers used include olefins having 2 to 16 carbon atoms. These high molecular weight polymers are applied to the backing material (silicone-coated kraf~
i paper) from heptane solutions containing 16 wt. % polymer. Only qualitative tests (such as touching the adhesive with a finger) are ~, .. . .
~ used to determine if the materials have pressure-sensitive properties.
;~~ It is apparent, therefore, that it would be an advance in the state of the art to prdvide a group of selected propylene copolymers 30 which are permanently tacky and meet the property requirements for a `
hot-melt, pressure-sensitive adhesive. `-''~
.-., ,~ ` ' ' ~ .
~ - 2 - ~
. .
10~;~400 Accordingly by the present invention there is provided a hot melt, pressure sensitive adhesive comprising an amorphous copolymer of at least one lower l-olefin selected from the group consisting of propylene and l-butene and at least one higher l-olefin selected from the group consisting of l-hexene, l-heptene, l-octene, l-nonene and l-decene, said copolymer containing 40 to 60 mole percent higher I-olefin and having a melt viscosity at 190C within the range of lO,000 cp. to ; 75,000 cp., a density within the range of 0.85 to 0.86, a glass transition temperature within the range of -30C to -45C, and having no melting point measurable b~ Differential Scanning Calorimetry.
In order to meet the critical requirements for use as a general purpose, pressure-sensitive adhesive, a material must:
~, l. Provide a peel strength of at least 2.5 lb./in -Pressure Sensitive Tape Council (PSTC) Test -l, "Peel Adhesion for Single Coated Tape, 180 Angle".
2. Provide shear adhesion or strength (holding power; static shear resistance) of ~l,000 min. when tested with l kg. load - PSTC-7.
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3. Provide a rolling ball tack value of 2 in. or less -PSTC-6, "Tack, Rolling Ball Method." ~
4. Have melt viscosity stability at application ~-temperatures such that melt viscosity will change <20% in 100 hr. - J. E. Dickert, P.T. Von Bramer, W. C. Cooper and H. L.
Overbay, Journal of the Technical Association of the Pulp and Paper Industry, 51, 64A (1968), and
Overbay, Journal of the Technical Association of the Pulp and Paper Industry, 51, 64A (1968), and
5. Not leave a residue when coated tapes are peeled from highly polished steel at 73F. - PSTC-l.
It has been found that only a very limited number of olefin copolymers will meet the above-cited property require-ments. Suitable copolymers include propylene/higher l-olefin and l-butene/higher l-olefin copolymer containing 40 - 60 mole % higher l-olefin. Operable l-olefin monomers include `
l-hexene, l-heptene, l-octene, l-nonene, and l-decene. Pro-polyene copolymers with ~40 mole ~ comonomer have poor tack and generally poor peel strength while those with ~60 mole %
comonomer have poor static shear strength and they leave a residue when tapes are peeled from polished steel plates.
In addition to the fact that suitable copolymers must contain 40-60 mole % comonomer, it is essential that the polymer molecule have a particular structure. For example, operable copolymers have no detectable crystallinity by either ~
X-ray or DSC techniques. ;
It was also found that Tg and density measurements ?
are useful for the characterization of useful copolymers.
One suitable method for measuring the Tg (glass transition temperature) of polymers is by Differential Scanning Calori-metry [John Mitchell and Jen Chiu, Anal. Chem. Annual Reviews, 43, 267R (1971); M. J. O'Neill and R. L. Fyans, "Design of Differential Scanning Calorimeters and the Performance of a ., _ 4 _ ~' ~
';'','`, ~241~0 New System", paper presented at the Eastern Analytical Symposium, New York City, November, 1971]. Density of polymers is gener-ally determined in a density gradient tube (ASTM Method D1505).
It has been found that useful copolymers have a density of .. ~ .. . .
~0.86 and a Tg intermediate between that observed for poly-propylene and that of the higher poly-l-olefin. For example, ~ polypropylene has a Tg of about -20C. and poly-l-hexene :' has a Tg of about -50C. (J. Brandrup and E. H. Immergut editors, "Polymer Handbook", Interscience Publishers, New York City, :
- 10 1966). Useful propylene/l-hexene copolymers containing 40~-60 , ,~ .
mole % l-hexene normally show Tg values of about -30 to -45C.
-~ If the copolymer is too "Blocky" (i.e., contains relatively: :
long segments of propylene), the copolymer will have a density ; o~ ~0.86 and it will show a Tg value characteristic of propylene ; homopolymer (e.g., about -15 to -20C.).
The NMR spectra can also be used to characterize ., 'f'~ the pressure-sensitive adhesives of this invention. For ~ example, carbon-13 NMR spectra of operable propylene/l-hexene .i :.
copolymers determined in a mixture of o-dichlorobenzene and -~ 20 deuterobenzene as solvent and hexamethyldisilo~ane as an , ...................................................................... .
internal standard shows a single peak at 12.2 ppm. and a multi-plicity of peaks centered at about 19.7, 18.9 and 18.1 ppm.
:. .
The single peak at 12.2 ppm. is due to the presence of the methyl group in the butyl side groups of the l-hexene monomer units. The three sets of multiplets are due to the methyl side groups of the propylene monomer units. There are three sets of multiplets since there are triads of propylene monomer units present in all three possible types of stereo-regular configurations ,(e.g. 111 or ddd triads, ddl or lld triads, and ldl or dld triads). These new pressure-sensitive adhesive `~
polymers appear to be multiblock copolymers of higher l-olefin ~ .
r ~ 5 ~ ~.
.~ .
.~ '1'' .
, 1~6Z4~0 .; . .
and propylene wherein the propylene blocks are partly stereore~ular and partly heterotactic segments which are pre- ;
dominantly ~20 monomer units long and wherein the higher 1-olefin blocks are incapable of crystallization at least over the use temperature range of -20 to 180F. We believe that while these copolymers show no detectable crystallinity by X-ray or DSC, they do contain a very low order of polypro-pylene-type crystallinity which accounts for their good co-hesive strength in pressure-sensitive adhesive applications.
This structural interpretation of these new pressure-sensitive copoLymers is supported by the measurable structure -dependent properties discussed below:
Melt viscosity range, cp. at 190C. 10,000-75,000 Composition range (hi~her l-olefin concentration in mole %) 40-60 :, ,: ...
Density range, g./cc 0.85-0.86 Tg range, C. (glass transition temperature) -30 to -45 Tm (crystalline melting point) no measurable ;~m Tm by DSC
:. ;.
- In addition to these structure-dependent properties, ~ 20 these pressure-sensitive adhesives can also be characterized ~ ~
',3 by functional properties which are determined on l-mil poly ~ -(ethylene terephthalate) films coated with 0.75-1.0-mil ad-hesive:
Rolling ball tack, in. ~2.0 Static shear strength range, minutes 1,000-4,000 ~, Peel strength range, lb./in. 2.5-5.0 In preparing these coated tapes, it is critical that the adhesive be applied to the poly(ethylene terephthalate) film at a melt temperature of at least 350F. The backing material may be preheated if it is polyester, cotton or paper.
Heat sensitive backing materials such as cellulose acetate or ',. ..
`- 1062400 cellophane are generally not preheated in order to prevent distortion of the backing. The adhesive coating thickness is also critical since commercial coating thickness is generally l-mil or less. Coating thicknesses of 2-3 mil give erroneous data concerning the utility of the polymer as a pressure-sensitive adhesive.
The type of catalyst and the polymerization conditions ,- .
required to provide copolymers having the desired structure are quite limited. In general~ the best results have been achieved by using catalyst systems which provide poor stereo-regulation in the polymerization of propylene. Combinations of Et3Al with AATiC13 with Al/Ti molar ratios ranging from about 1:1 to 5:1 have been found to be useful. It is also necessary to conduct the polymerization at high temperatures with the preferred temperature range being 150-160C. The operable temperature range is 140-170C. Temperatures below 140C provide too much blocking even when using Et3Al/AATiC1 ~y catalysts. The molecular weight (melt viscosity) of copolymers made at temperatures in excess of 170C is too low to provide ~, 20 adequate pressure-sensitive adhesive properties.
If catalysts which provide highly stereore~ular .. . ..
~1 propylene homopolymer are used to copolymerize propylene and ,1 hexene, multiblock copolymers are formed which contain crystallizable propylene segments. Thus, they have inadequate pressure-sensitive adhesive properties. Examples of highly ¦ stereospecific catalysts ~for the polymerization of propylene) ,~ which provide this result include EtAlC12/Bu3N/TiC13, I Et3Al/HPT/TiC13, and Et2AlCl/UPT/TiC13 catalysts. (Bu3N
refers to tributylamine and HPT refers to hexamethylphos-phorictriamide).
*AATiCl identifies TiC13 which has been prepared by reducing i TiC14 ~ith aluminum. -,;; '::
~6;~40~D ~
The preferred melt viscosity range for copolymers of this invention include about 13,000 to about 50,000 cp. at 190C. The operable melt viscosity range is 10,000 to 75,000 cp.
The olefin copolymer pressure-sensitive adhesives of this invention may be stabilized by the addition of conventional ~;
stabilizers for polyolefin materials such as dilauryl thio-dipropionate, Plastonox 1212 (lauryl stearyl thiodipropionate), ~ , .. .
Irganox 1010 ~pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]}, Eastman Inhibitor DOPC (diocta-decyl p-cresol), Plastonox 2246 [2,2'-methylene bis(4-methyl-
It has been found that only a very limited number of olefin copolymers will meet the above-cited property require-ments. Suitable copolymers include propylene/higher l-olefin and l-butene/higher l-olefin copolymer containing 40 - 60 mole % higher l-olefin. Operable l-olefin monomers include `
l-hexene, l-heptene, l-octene, l-nonene, and l-decene. Pro-polyene copolymers with ~40 mole ~ comonomer have poor tack and generally poor peel strength while those with ~60 mole %
comonomer have poor static shear strength and they leave a residue when tapes are peeled from polished steel plates.
In addition to the fact that suitable copolymers must contain 40-60 mole % comonomer, it is essential that the polymer molecule have a particular structure. For example, operable copolymers have no detectable crystallinity by either ~
X-ray or DSC techniques. ;
It was also found that Tg and density measurements ?
are useful for the characterization of useful copolymers.
One suitable method for measuring the Tg (glass transition temperature) of polymers is by Differential Scanning Calori-metry [John Mitchell and Jen Chiu, Anal. Chem. Annual Reviews, 43, 267R (1971); M. J. O'Neill and R. L. Fyans, "Design of Differential Scanning Calorimeters and the Performance of a ., _ 4 _ ~' ~
';'','`, ~241~0 New System", paper presented at the Eastern Analytical Symposium, New York City, November, 1971]. Density of polymers is gener-ally determined in a density gradient tube (ASTM Method D1505).
It has been found that useful copolymers have a density of .. ~ .. . .
~0.86 and a Tg intermediate between that observed for poly-propylene and that of the higher poly-l-olefin. For example, ~ polypropylene has a Tg of about -20C. and poly-l-hexene :' has a Tg of about -50C. (J. Brandrup and E. H. Immergut editors, "Polymer Handbook", Interscience Publishers, New York City, :
- 10 1966). Useful propylene/l-hexene copolymers containing 40~-60 , ,~ .
mole % l-hexene normally show Tg values of about -30 to -45C.
-~ If the copolymer is too "Blocky" (i.e., contains relatively: :
long segments of propylene), the copolymer will have a density ; o~ ~0.86 and it will show a Tg value characteristic of propylene ; homopolymer (e.g., about -15 to -20C.).
The NMR spectra can also be used to characterize ., 'f'~ the pressure-sensitive adhesives of this invention. For ~ example, carbon-13 NMR spectra of operable propylene/l-hexene .i :.
copolymers determined in a mixture of o-dichlorobenzene and -~ 20 deuterobenzene as solvent and hexamethyldisilo~ane as an , ...................................................................... .
internal standard shows a single peak at 12.2 ppm. and a multi-plicity of peaks centered at about 19.7, 18.9 and 18.1 ppm.
:. .
The single peak at 12.2 ppm. is due to the presence of the methyl group in the butyl side groups of the l-hexene monomer units. The three sets of multiplets are due to the methyl side groups of the propylene monomer units. There are three sets of multiplets since there are triads of propylene monomer units present in all three possible types of stereo-regular configurations ,(e.g. 111 or ddd triads, ddl or lld triads, and ldl or dld triads). These new pressure-sensitive adhesive `~
polymers appear to be multiblock copolymers of higher l-olefin ~ .
r ~ 5 ~ ~.
.~ .
.~ '1'' .
, 1~6Z4~0 .; . .
and propylene wherein the propylene blocks are partly stereore~ular and partly heterotactic segments which are pre- ;
dominantly ~20 monomer units long and wherein the higher 1-olefin blocks are incapable of crystallization at least over the use temperature range of -20 to 180F. We believe that while these copolymers show no detectable crystallinity by X-ray or DSC, they do contain a very low order of polypro-pylene-type crystallinity which accounts for their good co-hesive strength in pressure-sensitive adhesive applications.
This structural interpretation of these new pressure-sensitive copoLymers is supported by the measurable structure -dependent properties discussed below:
Melt viscosity range, cp. at 190C. 10,000-75,000 Composition range (hi~her l-olefin concentration in mole %) 40-60 :, ,: ...
Density range, g./cc 0.85-0.86 Tg range, C. (glass transition temperature) -30 to -45 Tm (crystalline melting point) no measurable ;~m Tm by DSC
:. ;.
- In addition to these structure-dependent properties, ~ 20 these pressure-sensitive adhesives can also be characterized ~ ~
',3 by functional properties which are determined on l-mil poly ~ -(ethylene terephthalate) films coated with 0.75-1.0-mil ad-hesive:
Rolling ball tack, in. ~2.0 Static shear strength range, minutes 1,000-4,000 ~, Peel strength range, lb./in. 2.5-5.0 In preparing these coated tapes, it is critical that the adhesive be applied to the poly(ethylene terephthalate) film at a melt temperature of at least 350F. The backing material may be preheated if it is polyester, cotton or paper.
Heat sensitive backing materials such as cellulose acetate or ',. ..
`- 1062400 cellophane are generally not preheated in order to prevent distortion of the backing. The adhesive coating thickness is also critical since commercial coating thickness is generally l-mil or less. Coating thicknesses of 2-3 mil give erroneous data concerning the utility of the polymer as a pressure-sensitive adhesive.
The type of catalyst and the polymerization conditions ,- .
required to provide copolymers having the desired structure are quite limited. In general~ the best results have been achieved by using catalyst systems which provide poor stereo-regulation in the polymerization of propylene. Combinations of Et3Al with AATiC13 with Al/Ti molar ratios ranging from about 1:1 to 5:1 have been found to be useful. It is also necessary to conduct the polymerization at high temperatures with the preferred temperature range being 150-160C. The operable temperature range is 140-170C. Temperatures below 140C provide too much blocking even when using Et3Al/AATiC1 ~y catalysts. The molecular weight (melt viscosity) of copolymers made at temperatures in excess of 170C is too low to provide ~, 20 adequate pressure-sensitive adhesive properties.
If catalysts which provide highly stereore~ular .. . ..
~1 propylene homopolymer are used to copolymerize propylene and ,1 hexene, multiblock copolymers are formed which contain crystallizable propylene segments. Thus, they have inadequate pressure-sensitive adhesive properties. Examples of highly ¦ stereospecific catalysts ~for the polymerization of propylene) ,~ which provide this result include EtAlC12/Bu3N/TiC13, I Et3Al/HPT/TiC13, and Et2AlCl/UPT/TiC13 catalysts. (Bu3N
refers to tributylamine and HPT refers to hexamethylphos-phorictriamide).
*AATiCl identifies TiC13 which has been prepared by reducing i TiC14 ~ith aluminum. -,;; '::
~6;~40~D ~
The preferred melt viscosity range for copolymers of this invention include about 13,000 to about 50,000 cp. at 190C. The operable melt viscosity range is 10,000 to 75,000 cp.
The olefin copolymer pressure-sensitive adhesives of this invention may be stabilized by the addition of conventional ~;
stabilizers for polyolefin materials such as dilauryl thio-dipropionate, Plastonox 1212 (lauryl stearyl thiodipropionate), ~ , .. .
Irganox 1010 ~pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]}, Eastman Inhibitor DOPC (diocta-decyl p-cresol), Plastonox 2246 [2,2'-methylene bis(4-methyl-
6-tert-butylphenol)], and ~thyl 702 [4,4'-methylene bis-(2,6-di-tert-butylphenol)], or combinations of such stabilizers.
Effective stabilizer concentrations may range from about 0.1 to about 0.5% by weight. For example, 0.25~ Irganox 1010 or a combination of 0.25~ Irganox 1010 with 0.25~ Plastonox 1212 f, . . .
provides good melt viscosity and color stability when the . ~ , , .
adhesive is maintained in molten form at 350~F. for 8 hours . or longer.
The olefin copolymer adhesives of the invention may be used alone or in mixture with other materials such as polyethylene waxes, polypropylene waxes, amorphous polypropylene, J, amorphous block ethylene/propylene copolymer, paraffin, poly-
Effective stabilizer concentrations may range from about 0.1 to about 0.5% by weight. For example, 0.25~ Irganox 1010 or a combination of 0.25~ Irganox 1010 with 0.25~ Plastonox 1212 f, . . .
provides good melt viscosity and color stability when the . ~ , , .
adhesive is maintained in molten form at 350~F. for 8 hours . or longer.
The olefin copolymer adhesives of the invention may be used alone or in mixture with other materials such as polyethylene waxes, polypropylene waxes, amorphous polypropylene, J, amorphous block ethylene/propylene copolymer, paraffin, poly-
7 terpenes;such as those commercially available .1 i,';
` 3 ,`
- 7a -~.' :, , : ~6240(~
` polyterpene tackifier resins, hydrocarbon resins such as hydrocarbon tackifier resins and the like.
This invention will be further illustrated by the following examples, although it will be understood that these examples are in-cluded merely for purposes of illustration and are not intended to limit the scope of the invention.
In a nitrogen filled dry box, 200 ml. of dry mineral spirits, 268 ml. of l-hexene (distilled and dried over sodium ribbon), and 0.37 g. AiATiC13 are placed into a clean, dry, 1-1 autoclave, equipped , with a stirrer. The autoclave is sealed in the dry box. A clean, `~
dry catalyst injector is loaded with 0.5 g. of Et3Al and 35 ml. of `.,~
dry mineral spirits in the dry box and then it is connected to the ~I autoclave. The molar ratio of Al to Ti in the catalyst is 2.4 to 1.
.., ~j After removing the autoclave from the dry box, 120 ml. of liquid propylene is pressured into the autoclave. This provides a monomer mixture containing 75 weight % l-hexene. The autoclave is . , -~ heated to 140C. with stirring. Then the Et3Al solution is injected into the monomer solution to initiate the copolymerization. The co-polylinerization is exothermic and the temperature of the reaction .... .
` mixture increases to 150C. This temperature is maintained for 3 ~' hours and then 200 ml. of isobutyl alcohol is pumped into the autoclave i to deactivate the catalyst. The temperature is maintained at 150C.
for an additional 15 minutes. Then the autoclave is cooled to 23C., vented, and the copolymer is placed in an excess of isobutyl alcohol.
~ The mixture is heated to 105C., cooled, filtered and the soft, ;~
¦ sticky, colorless copolymer is washed with additional isobutyl alcohol ,.. ..
to remove catalyst residues. The copolymer is stabilized with 0.25% ;
Irganox 1010 and dried in a vacuum oven at 70-80C. The yield of ~ ;
copolymer is 186 g. (77% conversion). It contains 43 mole % l-hexene `
,;. , (60 wt. % l-hexene) as determined by an NMR analysis. This tacky , copolymer has a melt viscosity of
` 3 ,`
- 7a -~.' :, , : ~6240(~
` polyterpene tackifier resins, hydrocarbon resins such as hydrocarbon tackifier resins and the like.
This invention will be further illustrated by the following examples, although it will be understood that these examples are in-cluded merely for purposes of illustration and are not intended to limit the scope of the invention.
In a nitrogen filled dry box, 200 ml. of dry mineral spirits, 268 ml. of l-hexene (distilled and dried over sodium ribbon), and 0.37 g. AiATiC13 are placed into a clean, dry, 1-1 autoclave, equipped , with a stirrer. The autoclave is sealed in the dry box. A clean, `~
dry catalyst injector is loaded with 0.5 g. of Et3Al and 35 ml. of `.,~
dry mineral spirits in the dry box and then it is connected to the ~I autoclave. The molar ratio of Al to Ti in the catalyst is 2.4 to 1.
.., ~j After removing the autoclave from the dry box, 120 ml. of liquid propylene is pressured into the autoclave. This provides a monomer mixture containing 75 weight % l-hexene. The autoclave is . , -~ heated to 140C. with stirring. Then the Et3Al solution is injected into the monomer solution to initiate the copolymerization. The co-polylinerization is exothermic and the temperature of the reaction .... .
` mixture increases to 150C. This temperature is maintained for 3 ~' hours and then 200 ml. of isobutyl alcohol is pumped into the autoclave i to deactivate the catalyst. The temperature is maintained at 150C.
for an additional 15 minutes. Then the autoclave is cooled to 23C., vented, and the copolymer is placed in an excess of isobutyl alcohol.
~ The mixture is heated to 105C., cooled, filtered and the soft, ;~
¦ sticky, colorless copolymer is washed with additional isobutyl alcohol ,.. ..
to remove catalyst residues. The copolymer is stabilized with 0.25% ;
Irganox 1010 and dried in a vacuum oven at 70-80C. The yield of ~ ;
copolymer is 186 g. (77% conversion). It contains 43 mole % l-hexene `
,;. , (60 wt. % l-hexene) as determined by an NMR analysis. This tacky , copolymer has a melt viscosity of
- 8 - ;
~.
~062~0 .
21, 300 cp. at 190C., an I.V. of 0.54, a Tg of -33C. and a density of 0.855. There is no detectable crystallinity in the sample by sither X-ray or DSC analysis.
The copolymer is heated to 177C. (350F.) and coated onto polyethylene terephthalate film by means of a hot Doctor blade to ~ Sauniform l-mil coating. This coated ~ ;
tape performs well as pressure-sensitive tape material. For :; -, . .
example, the polymer coating remains permanently tacky and it ~`~ has good adhesion to paper, steel, polyethylene, poly(ethylene terephthalate) and the like. When the tape is peeled away from a clean stainless s*eel surface, no polymer residue is left on the steel demonstrating that the copolymer has good -;~i cohesive strength. The tape has a rolling ball tack value of 3.8 cm. (1.5 in.), peel strength (on steel) of 3.1 lb./in.
and static shear strength (measured on steel using 1,000 g.
~i weight) of 3,596 min. When a torn page is mended with this tape, the printed matter under the tape is quite legible.
Similarly good results were obtained when the hot-melt, pressure-sensitive copolymer is coated on black paper, crepe paper, 60 lb. casein coated paper, cloth, cellophane, and cellulose acetate film backing materials.
The procedure of Example 1 is repeated except that a ~`
~,l different monomer ratio is used (300 ml. l-hexene and 87 ml.
propylene). The tacky, amorphous copolymer was obtained in ! 40% con~ersion and it has a melt viscosity of 23,500 cp. at ¦ 190C., an I.V. of 0~55 and a Tg of -40C. It contains 48 I mole ~ 1-hexene. Coated poly(ethylene terephthalate) tape 'l has a peel strength of 2.9 lb./in. width, rolling ball tack ~! ~
of 3.7 cm. and static shear strength of 1,658 minutes. This ;-copolymer also has pressure-sensitive adhesive properties.
.. .. . .
.; -.. .. . .
_ g _ ;'~.
:~0624Cl~
EX~MPLE 3 . _ .
Example 1 is followed, except that AATiC13/Et2AlCl/Bu3N
(1/0.75/0.75) catalyst is used at a polymerization temperature of 140C. The conversion of monomer to copolymer is 88%.
The product contains 46 mole % l-hexene, has a melt viscosity of 25,500 cp. at 190C., a density of 0.856, and a Tg of -16C.
This Tg value indicates the presence of substantial blocks of propylene monomer units. This "blockiness" probably accounts for the fact that coated poly~ethylene terephthalate) tape (with an adhesive thickness of 1 mil) has a rolling ball tack value o~ 6.2 cm. and a peel strength of only 2.0 lb./in.
Thus, the copolymer of this example is unsuitable as a pressure-sensitive adhesive for general purpose tape even though it contains a l-hexene concentration similar to that of the copolymer of Example 2.
The procedure of Example 1 is followed except that the molar ratio of Al/Ti in the catalyst is 0.67 to 1 instead of 2.4 to 1. The conversion of monomer to copolymer is 80~.
The copolymer has a melt viscosity of 23,500 cp. at l90~C., a density of 0.846, a Tg of -40C., and it contains 44 mole l-hexene. Coated poly(ethylene terephthalate) tape has a peel strength of 3.4 lb./in., a rolling ball tack of 4.7 cm.
and a static shear strength of 497 min. Thus, this copolymer has some desirable pressure-sensitive adhesive properties, but it is deficient in static shear strength. This example illustrates the critical nature of molar ratio of Et3Al to ;~
AATiC13 in providing copolymers which will meet all critical pressure-sensitive adhesive properties. ~ -EXAMPLE 5 t~' ' ' "
l-Hexene (in the absence of propylene) is polymerized '.' ' -` ~0~2~0 ~ ;;
`, according to the procedure of Example 1. The conversion of ' , monomer to polymer is 29~. The tacky, colorless poly-l-hexene '', .: .:
has a melt viscosity of 21,200 cp. at 190C., a ~ensity of 0.854, and Tg of -48C. Coated poly(ethylene terephthalate) ~,,'' ' tape has a rolling ball tack value of 1.3 cm. and a peel 7': strength of about 3.2 lb./in. However, in the peel strength 1, test, the adhesive fails and a polymer residue is left on .~. . .
the steel plate as the coated tape is peeled away. Also, the static shear strength of the tape;,is only about 100 min.
'' 10 Thus, this polymer is not a suitable pressure-sensitive ad-,,j hesive for general purpose tape applications.
'`'!~ EXAMPLE 6 .-,i, The procedure of Example 1 is followed, except that ~'~" a 90/10 weight ~ l-hexene/propylene monomer mixture is used.
,( The conversion of monomer to copolymer is 71%. The copolymer has a melt viscosity of 21,300 cp., at 190C., and it contains ' 65 mole ~ l-hexene. Coated poly(ethylene terephthalate) tape has a peel strength of 3.1 lb./in. width, rolling ball tack of 4.0 cm. and static shear strength of 124 min. Thus, this copolymer has inadequate static shear strength for general purpose pressure sensitive tape. ' :~ , .
,~, EXAMPLE 7 ,,~ The procedure of Example 1 is followed, except that ,ij 80/20 weight ~ l-hexene/propylene monomer mixture is used. '''I The conversion of monomer to copolymer is 75%. The copolymer ,' i:l has a melt viscosity of 28,000 cp. at 190C., and it contains ',' 58 mole percent l-hexene. Coated poly(ethylene terephthalate) 'j tape has a peel strength of 3.2 lb./in. width, ro~ling ball tack of 3.7 cm. and static shear strength of 1425 minutes. ' ' This copolymer has presusre-sensitive adhesive properties.
: .
~ , .
- 11 - ,,,: , ' `-~
The procedure of Example 1 is followed except that a monomer mixture containing 70 wt. % 1-hexene is used. The conversion of monomer to copolymer is 62%. The copolymer has a melt viscosity of 15,000 cp. at 190C., and it contains 37mole % l-hexene. Coated poly(ethylene terephthalate) tape has a peel strength of 3.6 lb./in. width, rolling ball tack ; of 4.0 cm. and static shear strength of about 843 min. Thus, this copolymer is borderline in static shear strength.
The procedure of Example 1 is followed, except that HATiC13 /Et3Al/HPT (1/0.75/0.75) catalyst and a 60/40 wt. %
~.~ . .. .
~ hexene/propylene monomer mixture are used. The conversion , ~ . . . .
of monomer to copolymer is 35%. The copolymer obtained has a melt viscosity of 495,000 cp. at 190C., and it contains ~?;
~!~ 18 mole % l-hexene. This copolymer contains crystallinity , which is characteristic of polypropylene (detected by -;~;, . ':
!' X-ray analysis) and it shows a Tm of 145C., and Tc of 102C.
~r by DSC analysis. It is nontacky and does not ~possess contact adhesion when coated poly(ethylene terephthalate) tape is touched to a steel plate~
Thus, copolymers containing relatively low concen-trations of l-hexene and which contain substantial amounts of crystallinity do not possess pressure-sensitive adhesive properties.
EX~MPLE 10 The procedure of Example 1 is repeated except that ..
the mole ratio of Al to Ti is 1 to 1. The copolymer (25,000 cp.
at 190C.) is obtained in 71~ conversion, and it contains 43 mole % l-hexene. It has a density of 0.856 and a Tg of i;.~. .
*HATiC13 identifies~TiC13 which has been prepared by reducing TiC1~ wi~h hydrogen.
;:
1~62~00 -37. Its pressure-sensitive adhesive properties are similar to those of the copolymer described in Example 1.
EXAMP~E 11 ., The procedure of Example 1 is repeated except that the mole ratio of Al to Ti is 5 to 1. The copolymer is obtained ; in 62~ conversion. Its physical properties and pressure-sensitive adhesive properties are similar to those of the i copolymer described in Example 1.
The procedure of Example 1 is followed except that the monomer mixture contains 8Q wt. ~ l-octene instead of -~ 75 wt. ~ l-hexene. The propylene/l-octene copolymer is obtained 0~
in a conversion of 69~. It contains 44 mole ~ l-octene and it i~ has a density of 0.854. Its pressure-sensitive adhesive properties are similar to those of the propylene/l-hexene copolymer described in Example 1.
Similar results are achieved when 80 wt. % l-decene ~, 1 is used instead of the l-octene.
.. . ............................................................... .
The procedure of Example 1 is followed except that ~,3A the monomer mixture contains 20 wt. ~ propylene, 40 wt. % -l-hexene and 40 weight ~ l-octene. The propylene/l-hexene/
l-octene terpolymer is obtained in 63% conversion. This tacky i copolymer has no detectable crystallinity by either DSC or X-ray analysist has a density of 0.854 and a Tg of -38. Its pressure-sensitive adhesive properties are similar to those of the propylene/l-hexene copolymer described in Example 1. ;
In a nitrogen filled dry box, 200 ml. of dry mineral `~
spirits, 125 ml. of l-hexene (distilled and dried over sodium ribbon), 155 ml. of dry l-octene, and 0.37 g. AATiC13 are placed into a clean, dry, l-liter autoclave, equipped with a ..
- 13 - ~
106Z~00 .
stirrer. The autoclave i5 sealed in the dry box. A clean, dry catalyst injector is loaded with 0.5 g. of Et3Al and 35 ml.
.:~
of dry mineral spirits in the dry box and then it is connected to the autoclave. The molar ratio of Al to Ti in the catalyst is 2.4 to 1.
. .: .
After removing the autoclave from the dry box, 116 ml.
, of liquid propylene is pressured into the autoclave. This provides a monomer mixture containing 76.5 weight ~ of higher -;
l-olefin. The autoclave is heated to 140C. with stirring.
Then the Et3Al solution is injected into the monomer solution to initiate the copolymerization. The copolymerization ~- is exothermic and the temperature of the reaction mixture in~
.,t,`,, creases to 150C. This temperature is maintained for 3 hours ~i ,~ , . . .
and then 200 ml. of isobutyl alcohol is pumped into the auto-clave to deactivate the catalyst. The temperature is main-tained at 150C. for an additional 15 minutes. Then the ~i autoclave is cooled to 23C.,;vented, and the copolymer is -~ placed in an excess of isobutyl alcohol. The mixture is ~
'' heated to 105C., cooled, fiItered and the soft, sticky, ~ -colorless copolymer is washed with additional isobutyl alcohol il ~ to remove catalyst residues. The copolymer is stabilized i~ with 0.25% Irganox 1010 and dried in a vacuum oven at 70-80C.
The yield of copolymer is 190 g. ~74~ conversion). It contains ', 50 mole ~ higher l-olefin (about 25 mole % l-hexene and about ,J 25 mole ~ l-octene) as determined by an NMR analysis. This ;l tacky copolymer has a melt viscosity of 26,000 cp. at 190C., a Tg of -38C. and a density of 0.85. There is no detectable crystallinity in the sample of either X-ray or DSC analysis.
The copolymer is heated to 177C. (350F.) and coated .~,j .: .
i 30 onto poly(ethylene terephthalate) film by means of a hot blade :;! to gi~e a uniform l-mil coating. This coated tape performs A ~ 14 i 11)6Z4~
well as pressure-sensitive tape material. For example, the polymer coating remains permanently tacky and it has good adhesion to paper, steeI, polyethylene, poly(ethylene~tere-phthalate) and the like. When the tape is peeled away from a clean stainless steel surface, no polymer residue is left on the steel demonstrating that the copolymer has good cohesive strength. The tape has a rolling ball tack value of 3.5 cm., peel strength ~on steel) of 3.4 lb./in. and static shear strength ~measured on steel using l,oO0 g. weight) of 4,000 min. When a torn page is mended with this tape, the printed matter under ~ . . . .
the tape is quite legible.
Similarly good results were obtained when the hot-melt, pressure-sensitive copolymer is coated on black paper, ~ crepe paper, 60-lb. Krome-Kote paper, cloth, cellophane, ;i and cellulose acetate film backing materials.
.
The procedure of Example 14 is repeated except that 116 ml. of propylene, 63 ml. of l-hexene, and 227 ml. of 1-octene are used. The~tacky, amorphous copolymer was obtained in 78% conversion and it has a melt viscosity of 23,500 cp.
at 190C., and a Tg of -40C. It contains 49 mole % propylen~
~, and 51 mole % higher l-olefin. Coated poly~ethylene tere-phthalate) tape has a peel strength of 3.2 lb./in. width, rolling ball tack of 3.4 cm. and static shear strength of ~ '.r 3,500 minutes. Thus, this copolymer also has good pressure-sensitive adhesive properties.
`: , ~ The procedure of Example 14 is followed, except that ! 96 ml. of propylene, 164 ml. of l-hexene, and 189 ml. of 1-octene are used. The conversion of monomer to copolymer is 75%. The copolymer has a melt viscosity of 28,000 cp. at 190C., and it contains 58 mole percent higher l-olefin.
.~:,. .
1~624~
.
; Coated poly(ethylene terephthalate~ tape has a peel strength of 3.2 lb./in. width, rolling ball tack of 3.7 cm. and static shear stength of 1425 minutes. This copolymer has pressure- -: .: . sensitive adhesive properties.
' EXAMPLE 17 The procedure of Example 14 is followed except that 196 ml. of propylene, 115 ml. of l-hexene, and 143 ml. of l-octene are used. The conversion of monomer to copolymer ~; is 68%. The copolymer has a melt viscosity of 25,000 cp.
.~" , .
~` 10 at 190C., and it contains 41 mole % higher I-olefins. Coated ~ poly(ethylene terephthalate) tape has a peel strength of ?' 3.6 lb./in. width, rolling ball tack of 4.0 cm. and static ;i shear strength of 1200 min.
The procedure of Example 14 is followed, except that ;
116 ml. of propylene, 125 ml. of l-hexene, 78 ml. of l-octene ~j~, . . .
and 95 ml. of l-decene are used. The conversion of monomer to copolymer is 70%. The copolymer obtained has a melt vis-.. ,; :
cosity of 28,000 cp. at 190C., and it contains 48 mole %
,~.. , , .
20 higher l-olefin. This copolymer has pressure-sensitive pro-perties similar to that of the copolymer described in Example 14.
,j --- ,. .
The procedure of Example 14 is repeated except that ~ 116 ml. of propylene, 155 ml. of l-octene, and 189 ml. of $ l-decene is used. The copolymer (25,000 cp. at 190C) is ;~
,.......
obtained in 71% conversion, and it contains 47 mole % higher !` .
I l-olefin. It has a density of 0.85 and a Tg of -37. Its pressuxe-sensitive adhesive properties are similar to those 3~ 30 of the copolymer described in Example 14. ;
.. . . .
,, ,;.. .
3 . : `
,.`'. . :' -, ,'.' ~'':.
_ 16 -`.
. , .... ..... ,....................................................... ~,~
24~
- The procedure of Example 14 is repeated except that - 116 ml. of propylene, 125 ml. of l-hexene and 140 ml. of 1-, :: , .
heptene are used. The copolymer is obtained in 70% conversion and contains about 50 mole ~ higher l-olefin. Its physical properties and pressure-sensitive adhesive properties are similar to those of the copolymer described in Example 14.
In a nitrogen filled dry box, 200 ml. of dry mineral spirits, 250 ml. ~168 g.) of 1 hexene (distilled and dried ..
',f- over sodium ribbon), and 0.37 g. AATiC13 are placed into a ~i; clean, dry, l-liter autoclave, equipped with a stirrer. The ,., autoclave is sealed in the dry box. A clean, dry catalyst injector is loaded with 0.5 g. of Et3A1 and 35 ml. of dry mineral spirits in the dry box and then it is connected to the ., .
autoclave. The molar ratio of Al to Ti in the catalyst is 2.4 to 1.
After removing the autoclave from the dry box, 120 ml.
(72 g.) of liquid 1-butene is pressured into the autoclave.
20 This provides a monomer mixture containing 70 weight ~ of 1-hexene. The autoclave is heated to 140C. with stirring.
i, :
Then the Et3Al solution is injected into the monomer solution to initiate the copolymerization. The copolymerization is ,.t exothermic and the temperature of the reaction mixture increases to 150C. This temperature is maintained for 3 i hours and then 200 ml. of isobutyl alcohol is pumped into the ~-autoclave to deactivate the catalyst. The temperature is maintained at 150C. for an additional 15 minutes. Then the i~
autoclave is cooled to 23C., vented, and the copolymer is X 30 placed in an excess of isobutyl alcohol. The mixture is ~-~
heated to 105C., cooled, filtered and the soft, sticky, 11~)6;~01D
.. . .
colorless copolymer is washed with additional isobutyl alcohol to remove catalyst residues. The copolymer is stabilized with 0.25% Irganox lOlO and dried in a vacuum oven at 70-80C.
The yield of copolymer is l90 g. (79% conversion). It contains 50 mole % l-hexene as determined by an NMR analysis. This tacky copolymer has a melt viscosity of 26,000 cp. at 190C., -a Tg of -40C. and a density of 0.85. There is no detectable crystallinity in the sample by either X-ray or DSC analysis.
The copolymer is heated to 177C. (350F.) and coated : . .
~lO onto poly(ethylene terephthalate) film by means of a hot blade to give a uniform l-mil coating. This coated tape performs : well as pressure-sensitive tape material. Por example, the polymer coatingremains permanently tacky and it has good ~ adhesion to paper, steel, polyethylene, poly(ethylene ;:
terephthalate) and the like. When the tape is peeled away from a clean stainless steel surface, no polymer residue is left on the steel demonstrating that thecoDolymer has good cohesive strength. The tape has a rolling ball tack value of 3.5 cm., peel strength (on steel) of 3.5 lb./in. and ~,20 static shear strength (measured on steel using l,000 g. weight) g of 4,200 min. When a torn page is mended with this tape, the printed matter under the tape is quite legible.
Similarly good results were obtained when the hot-melt, pressure-sensitive copolymer is coated on black paper, crepe paper, 60-lb~ Krome-Kote paper, cl~oth, cellophane, and cellulose acetate film backing materials.
!
The procedure of Example 21 is repeated except that 80 ml. of l-butene and 285 ml. of l-hexene are used. The ;~
~30 tacky, amorphous copolymer is obtained in 78% conversion and it has a melt viscosity of 23,000 cp. at 190C., and a Tg of ',' ,, :`
: ' ~062400 .. . .
-40C. It contains 59 mole % l-hexene. Coated poly(ethylene `~ terephthalate) tape has a peel strength of 3.2 lb./in. width rolling ball tack of 3.6 cm. and static shear strength of 2,200 mlnutes. Thus, this copolymer also has good pressure-sen~tive ~ adhesive properties.
'~- EXAMPLE 23 .~. .
The procedure of Example 21 is followed, except that 67 ml. of l-butene, 58 ml. of propylene, and 250 ml. of l-hexene are used. The conversion of monomer to copolymer ~` 10 is 75%. The copolymer has a melt viscosity of 28,000 cp.
at 190C., and it contains 50 mole percent l-hexene and about 25 mole % each of l-butene and propylene. Coated poly-~, (ethylene terephthalate) tape has a peel strength of 4.5 lb./in.
width, rolling ball tack of 2.3 cm. and static shear strength of 6500 minutes. This copolymer has excellent pressure-sen-;:...................................................................... .
-~3~ sitive adhesive propertiès.
~i EXAMPLE 24 The procedure of Example 21 is followed except that ~,.J~ ,.
160 ml. of l-butene and 214 ml. of l-hexene are used. The conversion of monomer to copolymer is 68%. The copolymer has a melt viscosity of 25,000 cp. at 190C., and it contains 40 mole % l-hexene. Coated poly(ethylene terephthalate) 3 tape has a peel strength of 3.6 lb./in. width, rolliny ball tack of 4.0 cm. and static shear strength of 3100 min.
``1 EXAMPLE 25 !i The procedure of Example 21 is followed, except that 120 ml. of l-butene, 125 ml. of l-hexene, and 155 ml. of ,~ l-octene are used. The conversion of monomer to copolymer ; is 70%. The copolymer obtained has a melt viscosity of 28,000 cp. at 190C., and it contains 48 mole % higher l-olefin.
~ This copolymer has pressure-sensitive properties similar to ,i ;' ,, -- 19 -- ~.
ial62~00 .... .
that of the copolymer described in Example 21.
: .
The procedure of Example 21 is repeated except that 120 ml. of l-butene, 155 ml. of l-octene, and 189 ml. of -l-decene are used. The copolymer (25,000 cp. at 190C.) is obtained in 71% conversion, and it contains 47 mole % higher l-olefin. It has a density of 0.85 and a Tg of -39C. Its pressure sensitive adhesive properties are similar to those of the copolymer described in Example 21.
EXAMæLE 27 The procedure of Exarnple 21 is repeated except that 120 ml. of l-butene, 125 ml. of l-hexene and 140 ml.
of l-heptene are used. The copolymer is obtained in 70%
conversion and contains about 50 mo~e % higher l-olefin. Its physical properties and pressure sensitive adhesive properties are simllar to those of the copolymer described in Example 21.
,, The procedure of Example 21 is repeated except that 120 ml. of l-butene and 311 ml. of l-octene are used. The copolymer is obtained in 78% conversion and it contains about 52 m~le % l-octene. Its physical properties and pressure sensitive adhesive properties are similar to that of the copolymer described in Example 21.
¦ The procedure of Example 21 is repeated except that i 120 ml. of l-butene, 125 ml. of l-hexene, 78 ml. of l-octene and 95 ml. of l-decene are used. The copolymer is obtained in 80% conversion, has a melt viscosity of 26,000 cp., and ~;~
contains 51 mole % higher l-olefin. Its physical properties and pressure sensitive properties are similar to that of the copolymer described in Example 21.
- 20 - ``
`,, ' Z4()0 ,"
The olefin ¢opolymer adhesives of this invention are useful as pressure sensitive adhesives. As pressure sen-sitive adhesives they find utility in preparing tapes by apply-;~ ing the adhesive by conventional means to a substrate such as a film which can be prepared from conventional film materials - such as a polyester, for example. The pressure sensitive adhesive can also be applied onto labels, decals, floor tile , , .
as well as wall coverings, such as wall paper, and shelf coverings~ such as shelf paper.
-; :
The invention has been described in considerable detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope ~ ...................................................................... . .
~l~ of the invention.
.";
". ''.
~h;
i, 20 :
, ~ .
''I .
~( .
.1 :
~, : ,:
~.
~062~0 .
21, 300 cp. at 190C., an I.V. of 0.54, a Tg of -33C. and a density of 0.855. There is no detectable crystallinity in the sample by sither X-ray or DSC analysis.
The copolymer is heated to 177C. (350F.) and coated onto polyethylene terephthalate film by means of a hot Doctor blade to ~ Sauniform l-mil coating. This coated ~ ;
tape performs well as pressure-sensitive tape material. For :; -, . .
example, the polymer coating remains permanently tacky and it ~`~ has good adhesion to paper, steel, polyethylene, poly(ethylene terephthalate) and the like. When the tape is peeled away from a clean stainless s*eel surface, no polymer residue is left on the steel demonstrating that the copolymer has good -;~i cohesive strength. The tape has a rolling ball tack value of 3.8 cm. (1.5 in.), peel strength (on steel) of 3.1 lb./in.
and static shear strength (measured on steel using 1,000 g.
~i weight) of 3,596 min. When a torn page is mended with this tape, the printed matter under the tape is quite legible.
Similarly good results were obtained when the hot-melt, pressure-sensitive copolymer is coated on black paper, crepe paper, 60 lb. casein coated paper, cloth, cellophane, and cellulose acetate film backing materials.
The procedure of Example 1 is repeated except that a ~`
~,l different monomer ratio is used (300 ml. l-hexene and 87 ml.
propylene). The tacky, amorphous copolymer was obtained in ! 40% con~ersion and it has a melt viscosity of 23,500 cp. at ¦ 190C., an I.V. of 0~55 and a Tg of -40C. It contains 48 I mole ~ 1-hexene. Coated poly(ethylene terephthalate) tape 'l has a peel strength of 2.9 lb./in. width, rolling ball tack ~! ~
of 3.7 cm. and static shear strength of 1,658 minutes. This ;-copolymer also has pressure-sensitive adhesive properties.
.. .. . .
.; -.. .. . .
_ g _ ;'~.
:~0624Cl~
EX~MPLE 3 . _ .
Example 1 is followed, except that AATiC13/Et2AlCl/Bu3N
(1/0.75/0.75) catalyst is used at a polymerization temperature of 140C. The conversion of monomer to copolymer is 88%.
The product contains 46 mole % l-hexene, has a melt viscosity of 25,500 cp. at 190C., a density of 0.856, and a Tg of -16C.
This Tg value indicates the presence of substantial blocks of propylene monomer units. This "blockiness" probably accounts for the fact that coated poly~ethylene terephthalate) tape (with an adhesive thickness of 1 mil) has a rolling ball tack value o~ 6.2 cm. and a peel strength of only 2.0 lb./in.
Thus, the copolymer of this example is unsuitable as a pressure-sensitive adhesive for general purpose tape even though it contains a l-hexene concentration similar to that of the copolymer of Example 2.
The procedure of Example 1 is followed except that the molar ratio of Al/Ti in the catalyst is 0.67 to 1 instead of 2.4 to 1. The conversion of monomer to copolymer is 80~.
The copolymer has a melt viscosity of 23,500 cp. at l90~C., a density of 0.846, a Tg of -40C., and it contains 44 mole l-hexene. Coated poly(ethylene terephthalate) tape has a peel strength of 3.4 lb./in., a rolling ball tack of 4.7 cm.
and a static shear strength of 497 min. Thus, this copolymer has some desirable pressure-sensitive adhesive properties, but it is deficient in static shear strength. This example illustrates the critical nature of molar ratio of Et3Al to ;~
AATiC13 in providing copolymers which will meet all critical pressure-sensitive adhesive properties. ~ -EXAMPLE 5 t~' ' ' "
l-Hexene (in the absence of propylene) is polymerized '.' ' -` ~0~2~0 ~ ;;
`, according to the procedure of Example 1. The conversion of ' , monomer to polymer is 29~. The tacky, colorless poly-l-hexene '', .: .:
has a melt viscosity of 21,200 cp. at 190C., a ~ensity of 0.854, and Tg of -48C. Coated poly(ethylene terephthalate) ~,,'' ' tape has a rolling ball tack value of 1.3 cm. and a peel 7': strength of about 3.2 lb./in. However, in the peel strength 1, test, the adhesive fails and a polymer residue is left on .~. . .
the steel plate as the coated tape is peeled away. Also, the static shear strength of the tape;,is only about 100 min.
'' 10 Thus, this polymer is not a suitable pressure-sensitive ad-,,j hesive for general purpose tape applications.
'`'!~ EXAMPLE 6 .-,i, The procedure of Example 1 is followed, except that ~'~" a 90/10 weight ~ l-hexene/propylene monomer mixture is used.
,( The conversion of monomer to copolymer is 71%. The copolymer has a melt viscosity of 21,300 cp., at 190C., and it contains ' 65 mole ~ l-hexene. Coated poly(ethylene terephthalate) tape has a peel strength of 3.1 lb./in. width, rolling ball tack of 4.0 cm. and static shear strength of 124 min. Thus, this copolymer has inadequate static shear strength for general purpose pressure sensitive tape. ' :~ , .
,~, EXAMPLE 7 ,,~ The procedure of Example 1 is followed, except that ,ij 80/20 weight ~ l-hexene/propylene monomer mixture is used. '''I The conversion of monomer to copolymer is 75%. The copolymer ,' i:l has a melt viscosity of 28,000 cp. at 190C., and it contains ',' 58 mole percent l-hexene. Coated poly(ethylene terephthalate) 'j tape has a peel strength of 3.2 lb./in. width, ro~ling ball tack of 3.7 cm. and static shear strength of 1425 minutes. ' ' This copolymer has presusre-sensitive adhesive properties.
: .
~ , .
- 11 - ,,,: , ' `-~
The procedure of Example 1 is followed except that a monomer mixture containing 70 wt. % 1-hexene is used. The conversion of monomer to copolymer is 62%. The copolymer has a melt viscosity of 15,000 cp. at 190C., and it contains 37mole % l-hexene. Coated poly(ethylene terephthalate) tape has a peel strength of 3.6 lb./in. width, rolling ball tack ; of 4.0 cm. and static shear strength of about 843 min. Thus, this copolymer is borderline in static shear strength.
The procedure of Example 1 is followed, except that HATiC13 /Et3Al/HPT (1/0.75/0.75) catalyst and a 60/40 wt. %
~.~ . .. .
~ hexene/propylene monomer mixture are used. The conversion , ~ . . . .
of monomer to copolymer is 35%. The copolymer obtained has a melt viscosity of 495,000 cp. at 190C., and it contains ~?;
~!~ 18 mole % l-hexene. This copolymer contains crystallinity , which is characteristic of polypropylene (detected by -;~;, . ':
!' X-ray analysis) and it shows a Tm of 145C., and Tc of 102C.
~r by DSC analysis. It is nontacky and does not ~possess contact adhesion when coated poly(ethylene terephthalate) tape is touched to a steel plate~
Thus, copolymers containing relatively low concen-trations of l-hexene and which contain substantial amounts of crystallinity do not possess pressure-sensitive adhesive properties.
EX~MPLE 10 The procedure of Example 1 is repeated except that ..
the mole ratio of Al to Ti is 1 to 1. The copolymer (25,000 cp.
at 190C.) is obtained in 71~ conversion, and it contains 43 mole % l-hexene. It has a density of 0.856 and a Tg of i;.~. .
*HATiC13 identifies~TiC13 which has been prepared by reducing TiC1~ wi~h hydrogen.
;:
1~62~00 -37. Its pressure-sensitive adhesive properties are similar to those of the copolymer described in Example 1.
EXAMP~E 11 ., The procedure of Example 1 is repeated except that the mole ratio of Al to Ti is 5 to 1. The copolymer is obtained ; in 62~ conversion. Its physical properties and pressure-sensitive adhesive properties are similar to those of the i copolymer described in Example 1.
The procedure of Example 1 is followed except that the monomer mixture contains 8Q wt. ~ l-octene instead of -~ 75 wt. ~ l-hexene. The propylene/l-octene copolymer is obtained 0~
in a conversion of 69~. It contains 44 mole ~ l-octene and it i~ has a density of 0.854. Its pressure-sensitive adhesive properties are similar to those of the propylene/l-hexene copolymer described in Example 1.
Similar results are achieved when 80 wt. % l-decene ~, 1 is used instead of the l-octene.
.. . ............................................................... .
The procedure of Example 1 is followed except that ~,3A the monomer mixture contains 20 wt. ~ propylene, 40 wt. % -l-hexene and 40 weight ~ l-octene. The propylene/l-hexene/
l-octene terpolymer is obtained in 63% conversion. This tacky i copolymer has no detectable crystallinity by either DSC or X-ray analysist has a density of 0.854 and a Tg of -38. Its pressure-sensitive adhesive properties are similar to those of the propylene/l-hexene copolymer described in Example 1. ;
In a nitrogen filled dry box, 200 ml. of dry mineral `~
spirits, 125 ml. of l-hexene (distilled and dried over sodium ribbon), 155 ml. of dry l-octene, and 0.37 g. AATiC13 are placed into a clean, dry, l-liter autoclave, equipped with a ..
- 13 - ~
106Z~00 .
stirrer. The autoclave i5 sealed in the dry box. A clean, dry catalyst injector is loaded with 0.5 g. of Et3Al and 35 ml.
.:~
of dry mineral spirits in the dry box and then it is connected to the autoclave. The molar ratio of Al to Ti in the catalyst is 2.4 to 1.
. .: .
After removing the autoclave from the dry box, 116 ml.
, of liquid propylene is pressured into the autoclave. This provides a monomer mixture containing 76.5 weight ~ of higher -;
l-olefin. The autoclave is heated to 140C. with stirring.
Then the Et3Al solution is injected into the monomer solution to initiate the copolymerization. The copolymerization ~- is exothermic and the temperature of the reaction mixture in~
.,t,`,, creases to 150C. This temperature is maintained for 3 hours ~i ,~ , . . .
and then 200 ml. of isobutyl alcohol is pumped into the auto-clave to deactivate the catalyst. The temperature is main-tained at 150C. for an additional 15 minutes. Then the ~i autoclave is cooled to 23C.,;vented, and the copolymer is -~ placed in an excess of isobutyl alcohol. The mixture is ~
'' heated to 105C., cooled, fiItered and the soft, sticky, ~ -colorless copolymer is washed with additional isobutyl alcohol il ~ to remove catalyst residues. The copolymer is stabilized i~ with 0.25% Irganox 1010 and dried in a vacuum oven at 70-80C.
The yield of copolymer is 190 g. ~74~ conversion). It contains ', 50 mole ~ higher l-olefin (about 25 mole % l-hexene and about ,J 25 mole ~ l-octene) as determined by an NMR analysis. This ;l tacky copolymer has a melt viscosity of 26,000 cp. at 190C., a Tg of -38C. and a density of 0.85. There is no detectable crystallinity in the sample of either X-ray or DSC analysis.
The copolymer is heated to 177C. (350F.) and coated .~,j .: .
i 30 onto poly(ethylene terephthalate) film by means of a hot blade :;! to gi~e a uniform l-mil coating. This coated tape performs A ~ 14 i 11)6Z4~
well as pressure-sensitive tape material. For example, the polymer coating remains permanently tacky and it has good adhesion to paper, steeI, polyethylene, poly(ethylene~tere-phthalate) and the like. When the tape is peeled away from a clean stainless steel surface, no polymer residue is left on the steel demonstrating that the copolymer has good cohesive strength. The tape has a rolling ball tack value of 3.5 cm., peel strength ~on steel) of 3.4 lb./in. and static shear strength ~measured on steel using l,oO0 g. weight) of 4,000 min. When a torn page is mended with this tape, the printed matter under ~ . . . .
the tape is quite legible.
Similarly good results were obtained when the hot-melt, pressure-sensitive copolymer is coated on black paper, ~ crepe paper, 60-lb. Krome-Kote paper, cloth, cellophane, ;i and cellulose acetate film backing materials.
.
The procedure of Example 14 is repeated except that 116 ml. of propylene, 63 ml. of l-hexene, and 227 ml. of 1-octene are used. The~tacky, amorphous copolymer was obtained in 78% conversion and it has a melt viscosity of 23,500 cp.
at 190C., and a Tg of -40C. It contains 49 mole % propylen~
~, and 51 mole % higher l-olefin. Coated poly~ethylene tere-phthalate) tape has a peel strength of 3.2 lb./in. width, rolling ball tack of 3.4 cm. and static shear strength of ~ '.r 3,500 minutes. Thus, this copolymer also has good pressure-sensitive adhesive properties.
`: , ~ The procedure of Example 14 is followed, except that ! 96 ml. of propylene, 164 ml. of l-hexene, and 189 ml. of 1-octene are used. The conversion of monomer to copolymer is 75%. The copolymer has a melt viscosity of 28,000 cp. at 190C., and it contains 58 mole percent higher l-olefin.
.~:,. .
1~624~
.
; Coated poly(ethylene terephthalate~ tape has a peel strength of 3.2 lb./in. width, rolling ball tack of 3.7 cm. and static shear stength of 1425 minutes. This copolymer has pressure- -: .: . sensitive adhesive properties.
' EXAMPLE 17 The procedure of Example 14 is followed except that 196 ml. of propylene, 115 ml. of l-hexene, and 143 ml. of l-octene are used. The conversion of monomer to copolymer ~; is 68%. The copolymer has a melt viscosity of 25,000 cp.
.~" , .
~` 10 at 190C., and it contains 41 mole % higher I-olefins. Coated ~ poly(ethylene terephthalate) tape has a peel strength of ?' 3.6 lb./in. width, rolling ball tack of 4.0 cm. and static ;i shear strength of 1200 min.
The procedure of Example 14 is followed, except that ;
116 ml. of propylene, 125 ml. of l-hexene, 78 ml. of l-octene ~j~, . . .
and 95 ml. of l-decene are used. The conversion of monomer to copolymer is 70%. The copolymer obtained has a melt vis-.. ,; :
cosity of 28,000 cp. at 190C., and it contains 48 mole %
,~.. , , .
20 higher l-olefin. This copolymer has pressure-sensitive pro-perties similar to that of the copolymer described in Example 14.
,j --- ,. .
The procedure of Example 14 is repeated except that ~ 116 ml. of propylene, 155 ml. of l-octene, and 189 ml. of $ l-decene is used. The copolymer (25,000 cp. at 190C) is ;~
,.......
obtained in 71% conversion, and it contains 47 mole % higher !` .
I l-olefin. It has a density of 0.85 and a Tg of -37. Its pressuxe-sensitive adhesive properties are similar to those 3~ 30 of the copolymer described in Example 14. ;
.. . . .
,, ,;.. .
3 . : `
,.`'. . :' -, ,'.' ~'':.
_ 16 -`.
. , .... ..... ,....................................................... ~,~
24~
- The procedure of Example 14 is repeated except that - 116 ml. of propylene, 125 ml. of l-hexene and 140 ml. of 1-, :: , .
heptene are used. The copolymer is obtained in 70% conversion and contains about 50 mole ~ higher l-olefin. Its physical properties and pressure-sensitive adhesive properties are similar to those of the copolymer described in Example 14.
In a nitrogen filled dry box, 200 ml. of dry mineral spirits, 250 ml. ~168 g.) of 1 hexene (distilled and dried ..
',f- over sodium ribbon), and 0.37 g. AATiC13 are placed into a ~i; clean, dry, l-liter autoclave, equipped with a stirrer. The ,., autoclave is sealed in the dry box. A clean, dry catalyst injector is loaded with 0.5 g. of Et3A1 and 35 ml. of dry mineral spirits in the dry box and then it is connected to the ., .
autoclave. The molar ratio of Al to Ti in the catalyst is 2.4 to 1.
After removing the autoclave from the dry box, 120 ml.
(72 g.) of liquid 1-butene is pressured into the autoclave.
20 This provides a monomer mixture containing 70 weight ~ of 1-hexene. The autoclave is heated to 140C. with stirring.
i, :
Then the Et3Al solution is injected into the monomer solution to initiate the copolymerization. The copolymerization is ,.t exothermic and the temperature of the reaction mixture increases to 150C. This temperature is maintained for 3 i hours and then 200 ml. of isobutyl alcohol is pumped into the ~-autoclave to deactivate the catalyst. The temperature is maintained at 150C. for an additional 15 minutes. Then the i~
autoclave is cooled to 23C., vented, and the copolymer is X 30 placed in an excess of isobutyl alcohol. The mixture is ~-~
heated to 105C., cooled, filtered and the soft, sticky, 11~)6;~01D
.. . .
colorless copolymer is washed with additional isobutyl alcohol to remove catalyst residues. The copolymer is stabilized with 0.25% Irganox lOlO and dried in a vacuum oven at 70-80C.
The yield of copolymer is l90 g. (79% conversion). It contains 50 mole % l-hexene as determined by an NMR analysis. This tacky copolymer has a melt viscosity of 26,000 cp. at 190C., -a Tg of -40C. and a density of 0.85. There is no detectable crystallinity in the sample by either X-ray or DSC analysis.
The copolymer is heated to 177C. (350F.) and coated : . .
~lO onto poly(ethylene terephthalate) film by means of a hot blade to give a uniform l-mil coating. This coated tape performs : well as pressure-sensitive tape material. Por example, the polymer coatingremains permanently tacky and it has good ~ adhesion to paper, steel, polyethylene, poly(ethylene ;:
terephthalate) and the like. When the tape is peeled away from a clean stainless steel surface, no polymer residue is left on the steel demonstrating that thecoDolymer has good cohesive strength. The tape has a rolling ball tack value of 3.5 cm., peel strength (on steel) of 3.5 lb./in. and ~,20 static shear strength (measured on steel using l,000 g. weight) g of 4,200 min. When a torn page is mended with this tape, the printed matter under the tape is quite legible.
Similarly good results were obtained when the hot-melt, pressure-sensitive copolymer is coated on black paper, crepe paper, 60-lb~ Krome-Kote paper, cl~oth, cellophane, and cellulose acetate film backing materials.
!
The procedure of Example 21 is repeated except that 80 ml. of l-butene and 285 ml. of l-hexene are used. The ;~
~30 tacky, amorphous copolymer is obtained in 78% conversion and it has a melt viscosity of 23,000 cp. at 190C., and a Tg of ',' ,, :`
: ' ~062400 .. . .
-40C. It contains 59 mole % l-hexene. Coated poly(ethylene `~ terephthalate) tape has a peel strength of 3.2 lb./in. width rolling ball tack of 3.6 cm. and static shear strength of 2,200 mlnutes. Thus, this copolymer also has good pressure-sen~tive ~ adhesive properties.
'~- EXAMPLE 23 .~. .
The procedure of Example 21 is followed, except that 67 ml. of l-butene, 58 ml. of propylene, and 250 ml. of l-hexene are used. The conversion of monomer to copolymer ~` 10 is 75%. The copolymer has a melt viscosity of 28,000 cp.
at 190C., and it contains 50 mole percent l-hexene and about 25 mole % each of l-butene and propylene. Coated poly-~, (ethylene terephthalate) tape has a peel strength of 4.5 lb./in.
width, rolling ball tack of 2.3 cm. and static shear strength of 6500 minutes. This copolymer has excellent pressure-sen-;:...................................................................... .
-~3~ sitive adhesive propertiès.
~i EXAMPLE 24 The procedure of Example 21 is followed except that ~,.J~ ,.
160 ml. of l-butene and 214 ml. of l-hexene are used. The conversion of monomer to copolymer is 68%. The copolymer has a melt viscosity of 25,000 cp. at 190C., and it contains 40 mole % l-hexene. Coated poly(ethylene terephthalate) 3 tape has a peel strength of 3.6 lb./in. width, rolliny ball tack of 4.0 cm. and static shear strength of 3100 min.
``1 EXAMPLE 25 !i The procedure of Example 21 is followed, except that 120 ml. of l-butene, 125 ml. of l-hexene, and 155 ml. of ,~ l-octene are used. The conversion of monomer to copolymer ; is 70%. The copolymer obtained has a melt viscosity of 28,000 cp. at 190C., and it contains 48 mole % higher l-olefin.
~ This copolymer has pressure-sensitive properties similar to ,i ;' ,, -- 19 -- ~.
ial62~00 .... .
that of the copolymer described in Example 21.
: .
The procedure of Example 21 is repeated except that 120 ml. of l-butene, 155 ml. of l-octene, and 189 ml. of -l-decene are used. The copolymer (25,000 cp. at 190C.) is obtained in 71% conversion, and it contains 47 mole % higher l-olefin. It has a density of 0.85 and a Tg of -39C. Its pressure sensitive adhesive properties are similar to those of the copolymer described in Example 21.
EXAMæLE 27 The procedure of Exarnple 21 is repeated except that 120 ml. of l-butene, 125 ml. of l-hexene and 140 ml.
of l-heptene are used. The copolymer is obtained in 70%
conversion and contains about 50 mo~e % higher l-olefin. Its physical properties and pressure sensitive adhesive properties are simllar to those of the copolymer described in Example 21.
,, The procedure of Example 21 is repeated except that 120 ml. of l-butene and 311 ml. of l-octene are used. The copolymer is obtained in 78% conversion and it contains about 52 m~le % l-octene. Its physical properties and pressure sensitive adhesive properties are similar to that of the copolymer described in Example 21.
¦ The procedure of Example 21 is repeated except that i 120 ml. of l-butene, 125 ml. of l-hexene, 78 ml. of l-octene and 95 ml. of l-decene are used. The copolymer is obtained in 80% conversion, has a melt viscosity of 26,000 cp., and ~;~
contains 51 mole % higher l-olefin. Its physical properties and pressure sensitive properties are similar to that of the copolymer described in Example 21.
- 20 - ``
`,, ' Z4()0 ,"
The olefin ¢opolymer adhesives of this invention are useful as pressure sensitive adhesives. As pressure sen-sitive adhesives they find utility in preparing tapes by apply-;~ ing the adhesive by conventional means to a substrate such as a film which can be prepared from conventional film materials - such as a polyester, for example. The pressure sensitive adhesive can also be applied onto labels, decals, floor tile , , .
as well as wall coverings, such as wall paper, and shelf coverings~ such as shelf paper.
-; :
The invention has been described in considerable detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope ~ ...................................................................... . .
~l~ of the invention.
.";
". ''.
~h;
i, 20 :
, ~ .
''I .
~( .
.1 :
~, : ,:
Claims (13)
1. A hot melt, pressure sensitive adhesive comprising an amorphous copolymer of at least one lower 1-olefin selected from the group consisting of propylene and 1-butene and at least one higher 1-olefin selected from the group consisting of 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene, said copolymer containing 40 to 60 mole percent higher 1-olefin and having a melt viscosity at 190°C within the range of 10,000 cp.
to 75,000 cp., a density within the range of 0.85 to 0.86, a glass transition temperature within the range of -30° to -45°C, and having no melting point measurable by Differential Scanning Calorimetry.
to 75,000 cp., a density within the range of 0.85 to 0.86, a glass transition temperature within the range of -30° to -45°C, and having no melting point measurable by Differential Scanning Calorimetry.
2. A hot melt, pressure sensitive adhesive comprising an amorphous 1-butene/higher 1-olefin copolymer containing 40 to 60 mole percent higher 1-olefin having a melt viscosity range at 190°C of 10,000 cp. to 75,000 cp., a density of 0.85 to 0.86, a glass transition temperature of -30 to -45°C., and having no melting point measurably by Differential Scanning Calorimetry, wherein said higher 1-olefin is a member of the group consisting of 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene.
3. A hot melt, pressure sensitive adhesive according to claim 2 wherein said amorphous 1-butene/higher 1-olefin copolymer is a 1-butene/1-hexene copolymer.
4. A hot melt, pressure sensitive adhesive according to claim 2 wherein said amorphous 1-butene/higher 1-olefin copolymer is a 1-butene/1-heptene copolymer.
5. A hot melt, pressure sensitive adhesive according to claim 2 wherein said amorphous 1-butene/higher 1-olefin copolymer is a 1-butene/1-octene copolymer.
6. A hot melt, pressure sensitive adhesive according to claim 2 wherein said amorphous 1-butene/higher 1-olefin copolymer is a 1-butene/1-nonene copolymer.
7. A hot melt, pressure sensitive adhesive according to claim 2 wherein said amorphous 1-butene/higher 1-olefin copolymer is a 1-butene/1-decene copolymer.
8. A hot melt, pressure sensitive adhesive comprising an amorphous propylene/higher 1-olefin copolymer containing 40 to 60 mole percent higher 1-olefin having a melt viscosity range at 190°C of 13,000 cp. to 50,000 cp., a density of 0.85 to 0.86, a glass transition temperature of -30 to -45°C., and having no melting point measurable by Differential Scanning Calorimetry, wherein said higher 1-olefin is a member of the group consisting of 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene.
9. A hot melt, pressure sensitive adhesive according to claim 8 wherein said amorphous propylene/higher 1-olefin copolymer is a propylene/1-hexene copolymer.
10. A hot melt, pressure sensitive adhesive according to claim 8 wherein said amorphous propylene/higher 1-olefin copolymer is a propylene/1-heptene copolymer.
11. A hot melt, pressure sensitive adhesive according to claim 8 wherein said amorphous propylene/higher 1-olefin copolymer is a propylene/1-octene copolymer.
12. A hot melt, pressure sensitive adhesive according to claim 8 wherein said amorphous propylene/higher 1-olefin copolymer is a propylene/1-nonene copolymer.
13. A hot melt, pressure sensitive adhesive according to claim 8 wherein said amorphous propylene/higher 1-olefin copolymer is a propylene/1-decene copolymer.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/563,534 US3954697A (en) | 1975-03-31 | 1975-03-31 | Poly(higher-1-olefin-co-propylene) copolymers as hot-melt, pressure-sensitive adhesives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1062400A true CA1062400A (en) | 1979-09-11 |
Family
ID=24250893
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA247,772A Expired CA1062400A (en) | 1975-03-31 | 1976-03-12 | Poly(higher-1-olefin-co-propylene) copolymers as hot-melt, pressure-sensitive adhesives |
Country Status (5)
| Country | Link |
|---|---|
| US (2) | US3954697A (en) |
| JP (1) | JPS5938277B2 (en) |
| CA (1) | CA1062400A (en) |
| GB (1) | GB1529895A (en) |
| IT (1) | IT1058911B (en) |
Families Citing this family (69)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4217428A (en) * | 1975-03-31 | 1980-08-12 | Eastman Kodak Company | Blends of substantially amorphous higher 1-olefin copolymers and tackifying resins useful as pressure-sensitive adhesives |
| US3954697A (en) * | 1975-03-31 | 1976-05-04 | Eastman Kodak Company | Poly(higher-1-olefin-co-propylene) copolymers as hot-melt, pressure-sensitive adhesives |
| US4072813A (en) * | 1976-02-11 | 1978-02-07 | Eastman Kodak Company | Poly(higher-1-olefin/1-butene) copolymers as hot-melt pressure-sensitive adhesives |
| US4178272A (en) * | 1977-03-02 | 1979-12-11 | Eastman Kodak Company | Hot-melt adhesvies for bonding polyethylene |
| US4169116A (en) * | 1977-11-07 | 1979-09-25 | Eastman Kodak Company | Blends of substantially amorphous olefin copolymers and compatible tackifying resins useful as hot-melt, pressure-sensitive adhesives |
| US4264756A (en) * | 1977-11-07 | 1981-04-28 | Eastman Kodak Company | Substantially amorphous olefin copolymers and compatible tackifying resins useful as hot-melt, pressure-sensitive adhesives |
| US4210570A (en) * | 1978-01-06 | 1980-07-01 | Eastman Kodak Company | Blends of substantially amorphous olefin copolymers, compatible tackifying resins and plasticizing oils useful as hot melt, pressure-sensitive adhesives |
| US4308361A (en) * | 1979-06-01 | 1981-12-29 | Mitsubishi Petrochemical Company, Ltd. | Propylene copolymers |
| US4259470A (en) * | 1979-08-30 | 1981-03-31 | Eastman Kodak Company | Propylene/1-butene or 1-pentene/higher 1-olefin copolymers useful as pressure-sensitive hot-melt adhesives |
| US4535140A (en) * | 1981-07-17 | 1985-08-13 | National Starch And Chemical Corporation | Hot-melt adhesives based on vinyl polymer |
| US4826939A (en) * | 1987-08-31 | 1989-05-02 | Eastman Kodak Company | Highly amorphous olefin terpolymer |
| JPS6442285U (en) * | 1987-09-08 | 1989-03-14 | ||
| CA1328447C (en) * | 1987-10-28 | 1994-04-12 | Horst Kurt Seeger | Catalysts for the preparation of amorphous copolymers of propylene and olefins |
| DE3888210T2 (en) * | 1987-11-30 | 1994-09-22 | Eastman Kodak Co | HOT MELT ADHESIVE. |
| US4886853A (en) * | 1987-11-30 | 1989-12-12 | Eastman Kodak Company | Hot-melt adhesive composition |
| US5021257A (en) * | 1987-11-30 | 1991-06-04 | Eastman Kodak Company | Hot-melt adhesive composition |
| US4929509A (en) * | 1988-07-06 | 1990-05-29 | Eastman Kodak Company | Adhesives based on amorphous propylene/hexene copolymers |
| US5112882A (en) * | 1989-09-06 | 1992-05-12 | Minnesota Mining And Manufacturing Company | Radiation curable polyolefin pressure sensitive adhesive |
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| US7265193B2 (en) * | 2003-01-31 | 2007-09-04 | Exxonmobil Chemical Patents Inc. | Polymerization process |
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| US20070270538A1 (en) * | 2006-05-19 | 2007-11-22 | Marc Stacey Somers | Elastomeric compositions comprising butyl rubber and propylene polymers |
| JP5481489B2 (en) * | 2008-11-19 | 2014-04-23 | エクソンモービル・ケミカル・パテンツ・インク | Adhesive composition and method for producing an adhesive composition |
| US20110059277A1 (en) * | 2009-09-04 | 2011-03-10 | Rainer Kolb | Elastomeric Surface Coatings for Plastic Articles |
| US20100316808A1 (en) * | 2009-06-16 | 2010-12-16 | Gregory Keith Hall | Polyolefin Compositions for Coating Applications |
| US9017593B2 (en) * | 2009-06-16 | 2015-04-28 | Exxonmobil Chemical Patents Inc. | Composite materials comprising propylene-based polymer blend coatings |
| US20100316820A1 (en) * | 2009-06-16 | 2010-12-16 | Rainer Kolb | Composite Materials Comprising Propylene-Based Polymer Blend Coatings |
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| US20170292047A1 (en) | 2016-04-12 | 2017-10-12 | Rextac Llc | Hexene-1 Containing Amorphous Polyalphaolefins For Improved Hot Melt Adhesives |
| US10752815B2 (en) | 2016-04-12 | 2020-08-25 | Rextac Llc | Low molecular weight butene-1-co-hexene-1 amorphous poly alpha olefins for hot-melt adhesives with enhanced properties |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA856337A (en) | 1970-11-17 | H. King Sherrill | Alpha-olefin copolymer adhesives | |
| GB1003632A (en) | 1963-05-02 | 1965-09-08 | Oxford Paper Co | Improvements in planograpic printing plates |
| US3367909A (en) * | 1963-10-24 | 1968-02-06 | Gulf Research Development Co | Poly-alpha-olefin heat seal composition |
| DE1594063A1 (en) * | 1965-08-27 | 1970-07-09 | Johnson & Johnson | Pressure-sensitive self-adhesive foils and tapes |
| US3635754A (en) * | 1966-01-21 | 1972-01-18 | Johnson & Johnson | Adhesive product |
| US3923758A (en) * | 1973-07-02 | 1975-12-02 | Eastman Kodak Co | Substantially hexane soluble propylene/butene-1 copolymer containing 30 to 75 weight percent butene-1 |
| US3954697A (en) * | 1975-03-31 | 1976-05-04 | Eastman Kodak Company | Poly(higher-1-olefin-co-propylene) copolymers as hot-melt, pressure-sensitive adhesives |
-
1975
- 1975-03-31 US US05/563,534 patent/US3954697A/en not_active Expired - Lifetime
-
1976
- 1976-02-02 US US05/654,317 patent/US4072812A/en not_active Expired - Lifetime
- 1976-03-12 CA CA247,772A patent/CA1062400A/en not_active Expired
- 1976-03-31 GB GB13040/76A patent/GB1529895A/en not_active Expired
- 1976-03-31 JP JP51035903A patent/JPS5938277B2/en not_active Expired
- 1976-03-31 IT IT21800/76A patent/IT1058911B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| US3954697A (en) | 1976-05-04 |
| IT1058911B (en) | 1982-05-10 |
| JPS51122136A (en) | 1976-10-26 |
| JPS5938277B2 (en) | 1984-09-14 |
| GB1529895A (en) | 1978-10-25 |
| US4072812A (en) | 1978-02-07 |
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