DE2721474A1 - MODIFIED POLYOLEFING MIXTURES WITH IMPROVED ADHESIVITY TO DIFFERENT SUBSTRATES AND THE COMPOSITE MATERIALS OBTAINED THEREOF - Google Patents

Description

Chemplex Company
3100 Golf Road, Rolling Meadows, Illinois, V.St.A.

Modified polyolefin blends with improved adhesive properties on different substrates and those obtained with them

Composite materials

The present invention relates to modified polyolefin mixtures which, among other desirable properties, in particular have extremely strong adhesiveness to various substrates, and it also includes the composite materials obtained therewith.

Although already several polymers-and resin mixtures have been brought as an adhesive with strong adhesiveness for various substrates in proposal, but these agents have not proven to be technically viable to the desired extent. D _e mgegenüber be made available by the present invention, modified polyolefin resins, etc. by a considerably improved adhesion to substrates such as polar polymers, metals, glass, paper, wood excellent.. These resins can be used in any conventional manner, and the typical application processes include laminating, extrusion, the coating, co-extrusion, powder coating, blow molding and more.

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It is known per se that laminates of polyolefins with dissimilar substrates have many desirable properties. These include heat sealability and barrier properties. However, it is often difficult to bond polyolefins to dissimilar substrates because of the differences in their physical and chemical structures. In order to overcome these sticking difficulties, it has already been proposed earlier to use either an adhesive layer between the polyolefin and the substrate, or a far more expensive, highly polar copolymer of the polyolefin, ζ.B. an ionomer resin to be used instead of the conventional [ olefin. This latter possible! However, speed has not brought the desired full success because, despite the fact that the ionomer resin can have good adhesive properties, the adhesive bond formed easily! is weakened by the action of moisture.

j Another way to improve the adhesive strength of a

Polyolefin on a substrate is made on the polyolefin backbone chain grafting polar functional groups. The most commonly used combination consists of polypropylene, on which maleic anhydride is grafted, as well as modifications of such combinations. The enamel grafting of maleic anhydride (which is the most economical process), however, causes a reduction in the Moldability, which makes the product difficult to process will.

In contrast, the modified polyolefin mixtures which form the subject of the present invention are now characterized in that they consist essentially of (A) about 0.1 to 95 parts by weight of a member of the group of substances which in turn consists of (1) graft copolymers about 1 wt 70-991999 "of a polyethylene backbone that with about 30 to 0.001 ^ -.. up to make up to a total of 100 i" - a polymerizable compound or sev-

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rer polymerizable compounds has been grafted, the

(a) one or more acyclic, carbocyclic, heterocyclic or polycyclic molecular components and

(b) one or more carboxylic anhydride-containing Rings contains or contain,

wherein the molecular constituents of (a) are bound to the ring or the rings (b) in 2 to 5 places, and (2) Pöxpf copolymers of about 50 to 99.998 wt. ^ of a polyolefin backbone, which with a combination of about 0.001 to 25 # by weight of one or more ethylenically-unsaturated Carbonsäureester and about 0.001 to 25 wt. ^ - has one or more polymerizable unsaturated compounds grafted, which - except to make up to a total of 100 i ».

(a) one or more acyclic, carbocyclic, heterocyclic or polycyclic molecular components and

(b) one or more rings containing carboxylic acid anhydride contains or contains,

wherein the molecular constituents of (a) are bound to the ring or the rings (b) at 2 to 5 positions, in mixture with

(B) about 99.9 to 5 parts by weight of a polyethylene resin selected from a member of the class, which in turn consists of homopolymers of ethylene, copolymers of ethylene and an alpha-olefin, Terpolymers of ethylene, an alpha-olefin and a diene and mixtures of these polyethylene resins.

The modified polyolefin blends of the invention with their excellent adhesiveness to, for example, those already mentioned above The substrates mentioned provide composite materials which have exceptionally good heat sealability. Furthermore the adhesive bond formed is hardly affected by moisture. Surprisingly, the bond strength is

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the blends better in an unexpectedly aynergistic manner than that of any component when it is on its own Is tested. This finding applies despite the fact that the concentration of the carboxylic acid anhydride in the mixtures is reduced by dilution with the ungrafted resin component.

The mixtures of the graft copolymer and the polyethylene resin, which are constructed according to the teaching of the invention have - as the inventors of the present invention have found considerable technical advantages over known systems, and these advantages include: the port case of the need to Having to use additional layers of adhesive when using unmodified polyolefins with dissimilar ones Wants to glue substrates; Advantages of an economic nature because of the elimination of the need for costly, highly polar ones Having to use copolymers of the polyolefins; excellent adhesive strength; Insensitivity of the adhesive connection between the modified polyolefins and various substrates against the action of moisture.

The term "polyolefin" as used in this description of the invention for the grafted backbone is intended to include polymers and copolymers of ethylene, propylene, butene and other unsaturated aliphatic hydrocarbons. For the purposes of the present invention, particularly recommendable ethylene homopolymers, which have been prepared by either low pressure or high pressure process (linear high density polyethylenes or branched low-density polyethylene), and further copolymers of ethylene with up to 40 wt. $ > Higher molecular weight olefins, such as propylene, 1-butene and 1-hexene, which can contain up to 5 1 » di- or triolefins, as used industrially in ethylene-propylene terpolymers, for example ethylidene norbornene, methylene norbornene, 1,4-heavadiene and vinyl norbornene. It is also sometimes advantageous to graft onto mixtures of two or more of the abovementioned homopolymers, copolymers and terpolymers.

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AA

The "polyolefin" is also advantageous for the mixed resin, and analogously it is sometimes advisable to use mixtures of two or more of the above-mentioned homopolymers, copolymers and terpolymers to be used as the mixed resin.

Among the polymerizable compounds with the carboxylic acid anhydride-containing rings defined above, there are compounds be understood in which the rings are simple rings, fused rings, bridged rings, spiro rings, direct linked rings, rings linked via aliphatic chain links can represent one or more oxygen or Contain sulfur atoms, or they can be combinations of the be the above ring arrangements. These compound classes are represented by the following structural formulas, which of course only serve the purpose of explanation, but are in no way intended to imply a restriction.

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simple

fused

j-Methylcyclohex- ^ en-i ^ - 1,2,3,4,5,8,9,10-octahydrodicarboxylic acid anhydride (4-MlHEÄ ) naphthalene-2,3-dicarboxylic acid-

anhydride

acyclic maleic anhydride

spiro ß-Oxa-i ^ -diketospiro-

annealed and bridged rings

Maleopimaric acid (M-PA)

bridged

y _i £ .2.1_7hept-5-en-2,3-dicarboxylic acid anhydride (NBDA) bridged

3107010 ^ 2.2.2_7oc t-5-en-2,3-dicarboxylic acid anhydride (BODA)

direct

bound and aromatic

4- (2-cyclopentenyl) -benzene-1,2-dicarboxylic acid anhydride

bridged, mixture of isomers

x-Methylbicyclo £ "2.2. ^ en-2,3-dicarboxylic acid anhydride (XMNA)

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The rings can contain 3, 4, 5, 6, 7 or 8 atoms, but in general 5- and 6-membered rings are preferably in ' Embossing. The monomer can contain aromatic rings, however at least one ring should be aliphatic in nature. The olefin bond is preferably not with the anhydride groups conjugated. The monomer can be used for the purposes of the invention if the olefin bond is conjugated, but in a different way, e.g. by alkyl substitution, is deactivated. As an example without any limiting meaning of such a conjugated, but deactivated; Monomers is the cyclohex-i-ene-1,2-dicarboxylic anhydride too to name.

To the / conjugated, unsaturated esters, which are for the Co- ' Suitable grafting with the cyclic, unsaturated carboxylic acid anhydrides of the present invention include dialkyl maleates, dialkyl fumarates, dialkyl itaconates, dialkyl mesaconates, ' Dialkyl citraconates, alkyl acrylates, alkyl crotonates, alkyl ligates and alkyl methacrylates, the term "alkyl" being aliphatic, arylaliphatic and cycloaliphatic groups each with 1 to 30 carbon atoms. '

In the production of the graft copolymers it is often recommended to have more than one monomer in either to use one or both classes of monomers in order to achieve the to regulate physical properties of the finished graft copolymers.

The process for the preparation of the graft copolymers the mixtures according to the invention generally consists in a mixture of the polymer or polymers and the monomer or monomers to be grafted on

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in a solvent or above the melting point of the polyolefin with or without a catalyst. This is how it is done Grafting or co-grafting in the presence of air, hydroporous oxides, other catalysts of the free radical type or in the essentially complete absence of these materials, the mixture at elevated temperatures and (if no solvent is used) preferably with action strong shear forces.

In the preparation of the graft copolymers according to the invention are used, the mixture of polyolefin or polyolefins and monomers or monomers in a solvent or heated above the melting point of the polyolefin to reaction temperatures and under reaction conditions, which are described in more detail below, and then the resulting graft copolymer is obtained or collected, to mix it with the polyethylene resin afterwards. The expression "won" or "collected" is intended to mean any arbitrary Working method or any system are understood, with the help of which the graft copolymer that he i

can be separated. Therefore, the term "recovering" or "collecting" also includes the recovery of the copolymers in the form of precipitated flakes, pellets, powders ; and the like.

Any representative of the known hydroperoxides which has a half-life of at least one minute at 145 ° C. can be used as the catalyst. Such hydroperoxides correspond to the general formula RO-OH, in which R stands for an organic radical. Suitable hydroperoxides include tert-butyl hydroperoxide, p-menthane hydroperoxide, pinane hydroperoxide and cumene hydroperoxide, but there are also other hydroperoxides known to those skilled in the art,

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in question. The increased temperatures cause a quick :

Decomposition of the hydroperoxide, which causes the reaction between :

catalytically accelerated the polyolefin and the monomer, '

to form the graft copolymer. .

Obviously, the more homogeneous the mixture is before heating, the less the mixing work which has to be expended for the solution or the molten mass. It has generally been found that in order to achieve a desired conversion j some form of mixing in the absence of a solution ^! j by means of is highly recommended , even if an equal- ! moderate mixture of all components of the mixture is formed before heating. Will not be a solvent! is used, the mixture should generally be heated to a temperature above about 130 ⁰ C, and it is advantageous to use a temperature between about 200 ⁰ C and about 36O ⁰ C. Temperatures which are considerably above about 36O ° C should generally be avoided to a falling significant decomposition of the polymeric ingredients to be prevented. The reaction time required is quite short and on the order of a few seconds to about 20 minutes, although extended heating times do not significantly affect the product and can be used if desired.

A convenient way of carrying out the grafting reaction is to premix the ingredients and then extrude the mixture through a heated extruder. Ee can \ other mixing devices such as a Brabender mixer, a Banbury mixer, mixing rolls and. Like., Are used for dae process. To an excessive increase in molecular weight with the attendant possibility of

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Occurrence of a certain crosslinking at the elevated temperatures To prevent this, it is advisable to carry out the reaction in a closed reaction vessel. A simple or Multi-screw extruder achieves this result without the use of any auxiliary equipment, and it exhibits for this reason it is a particularly suitable reaction vessel, although it is by no means necessary.

The resulting graft copolymers (which is intended to include the co-graft copolymers), which are used according to the invention in the mixtures, consist, as has been found, of about 70 to 99.999% by weight of the polyolefin and about 30 to 0.001% by weight of the polyolefin. Ji from the cyclic, unsaturated · _; Carboxylic acid anhydride or mixtures thereof with the unsaturated carboxylic acid esters, and these graft copolymers formed in this way, can be mixed with a large number of polyethylene resins in order to produce the adhesives of the present invention I

to create.

The polyolefin that is used to produce the graft polymers

the mixtures according to the invention s is used, from a j

Polyethylene homopolymer with a density of at least \

consist of about 0.910 to 0.965, and it can essentially be |

be linear or branched . If it is in linear form, ■

then the density is preferably about 0.940, and is;

if it is in a branched form, the density is preferably ^;

at least about 0.910 to 0.930. >

The polyolefin can also consist of a terpolymer, j e.g. one of ethylene, propylene and a cyclic or acyclic aliphatic diene or a mixture of To serve.

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To those in the graft copolymers according to the invention. excellent monomers include 4-methylcyclohex-4-en-1,2-dicarboxylic anhydride, Tetrahydrophthalic anhydride, x-Methylnorborn-5-en-2,3-dicarboxylic anhydride, norborn-5-en-2,3-dicarboxylic anhydride and bicyclo (2.2.2) oct-5-en-2,3-dicarboxylic anhydride as well as the metal salts thereof.

In the practice of the present invention, it is recommended to first prepare a modified polyolefin, wherein a graft monomer is grafted in high concentration, and then mix the modified polyolefin with a non-grafted polyolefin, so that in this way the amount of Graft copolymer can be set or monitored in the j mixture. This method is better than the j grafting a small amount of the grafting monomer to a polymer backbone, and the use of this material, since the method of grafting a small \ amount is not economical. The amount of the mixed graft polymer in the mixture is determined by the amount which is necessary to achieve maximum adhesion to the substrate to be used. These substrates include polar polymers, wood, metal, glass, cellophane, paper, and many other materials. j

The following examples illustrate the preparation of the graft copolymers of the mixtures according to the invention and the methods by which they are made.

example 1

An electrically heated mixing head from C. W. Brabender, Inc. was modified to hold pressure. This reactor was filled with a mixture of 8.36 parts NBDA, 0.68 Parts of tert-butyl hydroperoxide (TBHP) and 90.96 parts of one

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High density polyethylene powder, melt index (HLMI) 7, loaded. The reactor was sealed, Ge with nitrogen: flushed and placed under vacuum until it was free of Säuerstjff, and then heated to 260 ⁰ G. After 160 ° C. had been reached, stirring was started at a speed of 160 revolutions per minute. After 15 minutes, a long time maintaining a temperature of 26O ⁰ C, with stirring, with the number of revolutions of 160 was cooled down, the mixture is quenched in cold hexane, dissolved in trichlorobenzene at 130 ⁰ C, precipitated in cold methyl ethyl ketone and heated overnight at 95 ⁰ C and an abso - Dried under pressure of 0.2 mm of mercury. The product contained 1.68 wt. # NBDA ₁ as indicated by elemental analysis. The melt index of the product was 0.11. For products with a higher melt index, a reactor with stronger shear forces can be used, as is explained in Examples 2 to 12 below.

Example 2

The same apparatus used in Example 1 was charged with 8.36 parts of NBDA and 91.64 parts of the polyethylene of Example 1. The reaction conditions were now 300 to 31o ⁰ C at a stirring speed of 275 rpm for a reaction time of 15 minutes in an oxygen-free atmosphere. The product, which was obtained after the work-up carried out in the same manner, contained 4.75% by weight of # NBDA as the elemental analysis showed, and the melt index value (HIMI) was 1.83. At the higher temperature and the higher stirring speed, the graft copolymer content and the melt index value are higher.

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Examples 3 (comparative experiment) and 4

Under the same conditions as with the modification that the reaction times were in Example 2 5 minutes, was maleic anhydride (MA) and XMNA on a polyethylene, melt index (HLMI) 7, grafted, and there were obtained the results summarized in Table I results.

Anhy
drid Table I. 2.62
1.56 product
Melting
index at
game
No. MA
XMNA filled grafted
Anhydride anhydride
Weight # weight # 1.50
12.08 3
4th 5.00
9.08

The product obtained by grafting on XMNA is significantly easier to process than the product obtained by grafting on MA. The reaction with the MA was 15 minutes carried out as in Example 2, the melt index value of the resulting product was too low, but that he could have been measured.

Examples 5 to 7

Under the same conditions and in the same apparatus as in Example 2, several different cyclic and polycyclic anhydrides were grafted to polyethylene, the results summarized in Table II results were obtained. In all cases the melt index values (HIIfI) of the graft polymer product were higher than that of the starting polyethylene.

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Table II

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Filled-in grafted product play anhydride-anhydride * anhydride ** melting no. Monomeric weight / weight / weight index

5 XMNA 9.08 3.01 8.26 6th 4-MTHPA 8.47 1.11 20.38 7th BODA 9.08 3.98 9.01

♦ The quantities filled in are equimolar and 5.0% by weight of MA

equivalent to.

** After dissolution and precipitation as in Example 1 to remove monomers and remove ungrafted homopolymers,

Example 8

A mixture of 6.8 kg (15 pounds) of tetrahydrophthalic anhydride (THPA) and 68.0 kg (150 pounds) of a high density polyethylene (Sohmelt Index 7) is prepared by adding an acetone solution of the THPA to the powder of the higher polyethylene Density of Example 1 sprayed and then evaporated the solvent. A co-rotating twin-screw extruder with five heating zones is fed with this mixture. The feed rate is about 22.7 kg / hour. (50 pounds per hour = pph) and the speed of rotation of the screw 300 revolutions per minute. The temperature profile is as follows: Zone 1 = 200 ⁰ O; Zone 2 ₉₂₇₀ ⁰ C; Zone 3 = 32O ⁰ C; Zone 4 = 27O ⁰ C; Zone 5 = 230 ⁰ C, and the temperature of the extrusion mold (die) is 180 ⁰ O. In zone 2, a mixture of the catalyst (TBHP) and the solvent (o-dichlorobenzene, ODCB) is fed, namely the TBHP with a Speed of

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about 0.136 kg / hour (0.3 pph) and the ODCB at a rate of 1.41 kg / hr. (3.1 pph). The reaction mixture is freed from volatile constituents in zone 4.

The resulting polyethylene / THPA graft copolymer has the following characteristics:

incorporated amount of THPA in f> 0.5, melt index 0.24

Tensile yield kg / cm 320.6

(psi) 4560

Breaking strength kg / cm ² 231

(Tensile break) (psi) 3290

Stretch in # 850

Example 9

A blend of 6.8 kg (15 pounds) NBDA and 68 kg (150 pounds) high density polyethylene (melt index 7) is prepared by spraying an acetone solution of the NBDA onto the powdered high density polyethylene of Example 1 and then spraying the solvent evaporates. This mixture is fed into a co-rotating twin screw extruder which has five heating zones. The temperature profile is as follows: Zone 1 = 20O ⁰ C; Zone 2 = 27O ⁰ C; Zone 3 = 32O ⁰ C; Zone 4 = 27O ⁰ C; Zone 5 = 230 ° C, and the temperature of the extrusion die amounts to 180 ⁰ C. In zone 2 are about 0.181 kg / hr. (0.4 pph) TBHP and 2.13 kg / hr. (4.7 pph) ODCB fed. The reaction mixture is freed from volatile constituents in zone 4.

The resulting polyethylene / NBDA graft copolymer has the following properties :

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incorporated amount of NBDA in # 3.3 melt index 0.16

Yield strength kg / cm 283.3

(psi) 4o30

Breaking strength kg / cm ² 185

(psi) 2630

Elongation in Ji 400

Example 10

The high-density polyethylene (melt index 7) is fed into a co-rotating twin-screw extruder with five heating zones. The feed rate is about 22.7 kg / hour. (50 pph) and the rotation speed of the screw 225 revolutions per minute. The temperature profile is the following: Zone 1 = 200 ⁰ C; Zone 2 = 270 ^° C; Zone 3 = 320 ^° C; Zone 4 = 270 ° C; Zone 5 = 23O ⁰ C, and the temperature of the extrusion die amounts to 180 ⁰ C. In zone 2, a mixture of tert-butyl hydroperoxide and XMNA (TBHP) at a rate of about 2.72 kg / hr. (6 pph) XMNA and from 0.136 kg / hr. (0.3 pph) TBHP fed. The reaction mixture is freed from volatile constituents in zone 4.

The resulting polyethylene / XMNA graft copolymer has the following properties:

incorporated amount of XMNA in j6 1 »8

Melt index 0.28

Yield strength kg / cm 287.5

(psi) 4090

Breaking strength kg / cm ² 180

(psi) 2560

Elongation in Jt 1020

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Examples 11 and 12

High-density polyethylene (melt index 7) and tetrahydrophthalic anhydride or bicyclo (2.2.1) hept-5-en-2,3-dicarboxylic anhydride are fed as dry mixtures into a co-rotating twin-screw extruder, which has five heating zones. The feed rates are 22.7 kg / hour. (50 pph) resin and 2.27 kg / hr. (5 pph) anhydride. In zone 2, 1 wt. # Of a TBHP catalyst is fed as a 10% solution in ODCB. The speed of rotation of the screw is 300 revolutions per minute. The temperature profile is the following: Zone 1 = 200 ⁰ C; Zone 2 = 27O ⁰ C ;. Zone 3 = 320 ° C; Zone 4 = 27O ⁰ C; Zone 5 = 230 ^° C., and the temperature of the extrusion mold is 180 ^° C. The reaction mixture is freed from volatile constituents in the zone and then collected.

Example 13

A terpolymer of ethylene, propylene and a cyclic diene, as it is marketed under the name "Nordel 1500" (by the company EI DuPont de Nemours and Company), was given 9.0% by weight of XMNA among those given in the example conditions grafted with the modification DAFL no catalyst was included. The product contained 1.8 Ji of grafted XMNA. In this way, EPD terpolymer elastomers can be used for the purposes of the present invention.

Example 14

A mixture of 80% by weight of high density polyethylene (HDPE) melt index 7 and 20 % by weight of "Nordel 1500" was grafted with 8.8% by weight of Ji XMNA under the same conditions as in Example 1 £. The product contained 2.2 parts by weight of grafted XMNA

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and had a melt index of 1.4. Mixtures of polyolefins can also be used for the purposes of the present invention Invention can be used.

Examples 15-17

A high-density ethylene-hexene copolymer (melt index 8; density 0.943) is fed into a co-rotating twin-screw extruder which has five heating zones. The feed rate is about 22.7 kg / h <(50 pph ) and the speed of rotation of the screws 250 revolutions per minute. The temperature profile is the following: Zone 1 = 200 ⁰ C; Zone 2 = 270 ⁰ C; Zone 3 = 320 ⁰ C; Zone 4 = 270 ⁰ C Zone 5 = 23 0 ⁰ C; the extrusion temperature is 180 ° C. The monomer or monomers with the dissolved catalyst are introduced at the same rates into zones 2 and 3. The mixture is freed from volatile constituents in zone 4.

The concentrations of the monomer feeds and the properties of the graft copolymers are as follows compiled in tabular form:

Tabel feed DBM
Gew.ji TBHP
Weight # III ZMNA DBM XMNA
Weight % none
4.9
15.2 none
0.25
0.75 1.2
1.5
1.4 none
0.2
1.1 at
game
No. 3.8
3.0
3.0 15th
16
17th Graft Mi schpolmerisate Melting
index 0.66
0.83
0.64

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It follows that the co-grafting can easily be carried out with XMNA and di-butyl maleate (DBM).

Example 18

An electrically heated mixing head from CW Brabender, Inc. was modified so that it could hold pressure. This reactor was charged with a mixture of 5.0 parts of NBDA, 5.0 parts of diethyl fumarate (DEP), 0.1 part of TBHP and 89.9 parts of a high density polyethylene (melt index 7). The reactor was sealed, purged with nitrogen and placed under vacuum until it was free from oxygen substantially and heated to 300 ⁰ C. Stirring was initiated at a rotational speed of 275 rpm when the temperature had reached 160 ⁰ C. After 15 minutes, a long holding a temperature of 300 ⁰ C at a rotational speed of 275 revolutions per minute was taken out the mixture from the reactor, quenched in hexane, dissolved at 130 ⁰ C in trichlorobenzene, precipitated in cold methyl ethyl ketone and at 95 ° C and dried overnight at an absolute pressure of 0.2 mm of mercury. The precipitated product contained 2.3% by weight of NBDA monomers and 1.7% by weight of DEF monomers. The melt index of the crude product was 10.8. Co-grafting can then be carried out just as easily with NBDA and DEF as with XMNA and DBM.

For the preparation of the mixtures according to the invention from the abovementioned graft copolymers and the polyethylene resin or the polyethylene resins, any mixing device or technique can be used. Just as an example note that all mixtures are applied in an electrically heated Brabender Plastioorder mixer head a screw mixer and observing the following

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Conditions were prepared: temperature 177 ⁰ G (35O ⁰ P); Rotor speed 120 revolutions per minute and mixing time 5 minutes after softening.

The mixtures were then transferred at 177 ⁰ C (35O ⁰ P) by compression molding in films of approximately 0.152 mm (0.006 inch) thickness. The films were then molding press Pasadena, exhibited in a hydraulic plates of format 20.32 χ 20,32 cm, on the substrate, which should be evaluated pressed. The test samples were held for 3 minutes at 204 ° C (400 ⁰ F) under a pressure of 70.3 kg / cm ² (1000 psig, and then followed quenching in a cold hydraulic Pasadena press under a Pressure was maintained at 281 kg / cm (4000 psig) Slip sheets were placed between the mix and the substrate to provide a tear strip for subsequent testing of the composite.

The resulting composites were cut into strips varying from 1.587 mm to 12.7 mm (1/16 "- 1/2") in width for testing. The tear strip of the test substrate was attached to a solid base, and weights were hung in a row increasing by 50 grams from the tear strip of the test film, which formed a lifting angle of 180 °. Attempts have been made to maintain a 90 ° angle between the angle of lift and the composite material being tested. The width of the test strip and the number of weights that were necessary to completely separate the composite material were recorded in each case.

The T-lift test described above is similar to the test that Dickert and coworkers in Tappi, Volume 51, No. 6 of June 1968 on page 66 A, apart from

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that weights of 30 grams were used in the Tapi test and that a 1-minute interval was observed before the next Weight was hung. The breaking point in the

findern test is the real number of weights that have been hung on the sample, and it is not half the final weight has been deducted as described by Dickert and co-workers.

The procedure described here is also somewhat related to ASTM regulation D 1876-72 for testing the T-peel strength of adhesives, but has the following differences:

1. ASTM regulation D 1876-72 uses a motor-driven Instrument used and the test panel is 12 inches long and 6 inches wide. The first 7.62 cm (3 inches) of the length are bent back to form a 90 ° bend.

2. The adhesive bond separation speed is 12.7 cm (5 inches) per minute.

3. The width of the strip is 2.54 cm (one inch).

4. Lift strength is determined from the autograph curve for the first 12.7 cm (5 inches) of lift after the initial peak.

5. The average lift-off load, in pounds per inch of width of the sample, required to separate the bonded bodies is recorded.

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$ 2

Example 19

XMNA is reacted with a high density polyethylene homopolymer resin in a twin screw extruder to produce a Graft copolymer resin, incorporated into the 1.0% by weight of XMNA and which has a melt index of 0.8 g / 10 min., to be obtained. The graft copolymer obtained in this way is mixed in varying amounts with a high-density polyethylene homopolymer resin with a melt index of 0.21 g / 10 min. and the density of which is 0.96 g / cc, mixed using the procedure described above. The mixtures and that too Graft copolymer resin itself and the high density polyethylene homopolymer resin itself are affected by their adhesiveness on a nylon 6 pile using the method above procedure described. The results obtained are summarized below:

Adhesion strength to nylon 6

Graft copolymer number of weights number of weight

as a mixture (1.587 mm (1/16 ") - (12.7 mm (1/2") - (wt. *) strips) strips)

0 <1 <1

5 11 <11

10 4 <11

25 3 11

50 3 9

75 2 6

90 <1 3

100 <1 2

As can be seen from the table, the adhesiveness of the mixtures surprisingly better ale that of a each component when it is tested alone. This statement applies despite the fact that the concentration of the anhydride in the mixtures is reduced by diluting the ungrafted resin component.

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Example 20

The graft copolymer resin described in Example 19 is in 3 wt. # - quantity range with an ethylene-hexene (1) copolymer resin, Melt index 0.26 g / 10 min. And density 0.95 g / ccm, mixed. Daa mixture and also the graft copolymer resin itself and the ethylene-hexene (I) copolymer resin themselves are tested for their adhesive strength on a nylon 6 pile and on an aluminum foil and the obtained Results are summarized below:

Adhesion to Adhesion to

Nylon 6 aluminum

Graft copolymer number of weights number of weights

as a mixture (1.587 mm (1/16 ") - (1.587 mm (1/16") -

(Gew.jS) stripes) stripes)

0 <1 <1

3> 11 6

100 <; 1 4

As can be seen from the above numerical values, alpha-olefin copolymers of ethylene can be used as mixed resins with excellent results. In addition , the bond strength of the mixture is better than that of any component when tested alone on different substrates, such as nylon and aluminum.

Example 21

The graft Mischpolymerisatharz described in Example 19 in 5 Gew.jt amount area with an ethylene-propyl ene diene Terpolymerisatharz as it is marketed under the name "Epeyn 5509" by the company Copolymer Rubber and Chemical Corporation, mixed . The mixture, as well as the graft copolymer resin itself and the BPDM resin itself, are tested for their adhesive strength to a nylon 6 film

tested. The results obtained are summarized below: _

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Grafted copolymer adhesive strength to nylon 6

in admixture number of weights (^ wt.) (1.587 mm (1/16 ") -St: mature)

0 <1

5 8

100 <1

As can be seen from the above numerical values, Terpolymerlsate of ethylene, an alpha-olefin and a diene can be used as mixed resins with excellent results.

Example 22

The graft copolymer described in Example 19 is mixed in a quantity of 3% by weight with a low-density polyethylene homopolymer resin, melt index 3.4 g / 10 min. And density 0.935 g / ccm. The mixture and also the graft copolymer resin itself and also the low-density polyethylene resin itself are tested for their adhesion to a nylon 6 pile and an aluminum foil. The results obtained are summarized below:

Adhesion to Adhesion to

Nylon 6 aluminum

Graft copolymer number of weights number of weights

as a mixture (1.587 mm (1/16 ") - (1.587 mm (1/16") - (wt. *) strips) strips )

0 <1 < 1

3 4 7

100 < 1 4

As the above numerical values show, homopolymers of low density ethylene can also be included

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272U7A

Results can be used as mixed resins. Again, the bond strength of the mixture is better than that of one each component when tested alone on different substrates such as nylon and aluminum.

Example 23

XMNA is reacted together with dibutyl maleate (DBM) with an ethylene-butene (1) mixed polymer resin in a twin-screw extruder to form a co-grafted mixed polymer resin into which 1.4% by weight of XMNA and 1.1% by weight of DBM are incorporated and which has a melt index of 0.64 g / 10 min. The graft copolymer described above is in the 3 wt ^ - ζ (1) -Mischpolymer ieathar amount region with an ethylene-hexene, melt index 0 _f 26 g / 10 min and density 0.95 g / cc, blended... The mixture and also the graft copolymer resin itself and also the propylene-hexene copolymer resin itself are tested for their adhesive strength on a nylon 6 pile. The results obtained are summarized below:

Grafted copolymer adhesive strength to nylon 6

in the mixture number of weights (weight *) (1,587 mm (1/16 ") - Strelfen )

0 <1

3 7

100 <1

The numerical values given above show that alpha-olefin copolymers of ethylene, which are co-grafted with an unsaturated carboxylic acid anhydride together with an ester monomer , can be used with excellent results as a graft copolymer component.

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272U7A

- 26 -

Example 24

The graft copolymer resin described in Example 19 is in the 5 wt. # range with a polyethylene homopolymer resin high density, melt index 0.21g / 10 min. and density 0.96 g / ccm, mixed. The mixture is just like an ionomer resin, which is sold under the name "Surlyn 1652" by the DuPont company on its adhesive strength a nylon 6 film tested. It lies in the form in which it is 5 weights are required to remove a 1.587 mm (1/16 ") strip of the ionomer resin from the nylon film separate, and 11 weights are required to remove a 1.587 mm strip of the graft copolymer mixture from Separate nylon film. If a drop of water is placed on the point of separation of the test film and the nylon film, it is enough 1 weight is required to completely separate the ionomer resin film from the nylon film, whereas 11 weights are required are to the film of the graft copolymer mixture from the nylon film with or without separating the drop of water. This demonstrates that the bond between the ionomer resin and the Nylon is easily affected by moisture, whereas the adhesive bond that is made between the Graft copolymer mixtures and the nylon has been formed, by which moisture is hardly affected.

Example 25

The graft copolymer described in Example 19 in a mixture of 30 wt.% Of a terpolymer of ethylene, propylene and ethylidene norbornene (EPDM) and 70 wt. # Of a high density (HDPE) polyethylene having a melt index of 13 and a density of 0.954 mixed in. The graft copolymer itself, the mixture of the two polymers and the

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Graft copolymer mixture were tested for their adhesive strength tested on an aluminum foil and the following results were obtained:

Adhesion strength

Graft-mixed aluminum polymer number of weights in the mixture HDPE-EPDM- (1.587 mm (1/1 &") - (weight #) mixture strips)

0 100 <j 1

3 97 8

100 0 4

The results illustrate that blends of an ethylene propylene terpolymer and a high density polyethylene can be used as mixed resins with excellent results. Again, the bond strength of the blend is found to be better than that of either component when tested alone.

All parts and percentages given in the description of the invention are parts by weight and percentages by weight.

80984 & / 04Ö8

Claims (38)

Pat ent claims 1. Modified polyolefin blends with improved adhesiveness on different substrates, characterized in that they consist essentially of (A) about 0.1 to 95 parts by weight of a representative of the group of substances which in turn consists of (1) Graft copolymers of about 70 to 99.999 wt. $> Of a polyethylene backbone that has been grafted with about 30 to 0.001 wt (a) one or more acyclic, carbocyclic, heterocyclic or polycyclic molecular components and (b) contains or contain one or more rings containing carboxylic acid anhydride, wherein the molecular constituents of (a) are bound to the ring or the rings (b) at 2 to 5 positions are and (2) graft copolymers of about 50 to 99.998 Gew.96 a polyolefin backbone that with a combination of about 0.001 to 25 Gew.96 of one or more ethylenically-unsaturated Carbonsäureester and about 0.001 to 25 weight i. "- to Supplement to a total of 100 96 - one or more polymerizable unsaturated compounds that has been grafted (a) one or more acyclic, carbocyclic, heterocyclic or polycyclic molecular components and (b) contains one or more rings containing carboxylic acid anhydride _; wherein the molecular constituents of (a) are bound to the ring or the rings (b) at 2 to 5 positions,
in mixture with 809846/0408 * 272U74 - 29 - (B) about 99.9 to 5 parts by weight of a polyethylene resin selected from a member of the class, which in turn consists of homopolymers of ethylene, copolymers of ethylene and one alpha-olefin, terpolymers of ethylene, an alpha-olefin and a diene and their mixtures Polyethylene resins. 2. Mixture according to claim 1, characterized in that said resin component (B) consists of an ethylene homopolymer consists. 3. Mixture according to claim 1, characterized in that said resin component (B) consists of a copolymer Ethylene and an alpha-olefin. 4. Mixture according to claim 1, characterized in that said resin component (B) is made from a polymer Ethylene, an alpha-olefin and a diene. 5. Miseh / ^ iH & äß claim 2, characterized in that said component (B) consists of a polyethylene with a density of about 0.910 to 0.965. 6. Mixture according to claim 1, characterized in that said component (B) consists of a linear copolymer of at least 60 weight # of ethylene and up to 40 wt. # Up to a total of 100 i » - an alpha-olefin with 4 to Consists of 6 carbon atoms, 7 · mixture according to claim 1, characterized in that said component (B) consists of a terpolymer of ethylene, propylene and up to 5 wt $> -.. Up to make up to a total of 100 wt i> -one cyclic or acyclic aliphatic diene or a mixture thereof. 8. Mixture according to claim 1, characterized in that said component (B) consists of a mixture of ethylene polymers, Ethylene-alpha-olefin copolymers and ethylene-propylene-diene terpolymers. 809846/0401 _ "_ 272U7 * 9. Mixture according to claim 1, characterized in that the said component (B) from a mixture of ethylene polymers and ethylene-alpha-olefin copolymers consists. 10. Mixture according to claim 1, characterized in that the said graft copolymer of component (A) of a polyethylene polymer and 4-methylcyclohex-4-ene-1,2-dicarboxylic anhydride consists. 11. Mixture according to claim 1, characterized in that, the said component (B) from a mixture of ethylene polymers and ethylene-propylene-diene terpolymers consists. 12. Geraisch according to claim 1, characterized in that the said graft copolymer of component (A) of a polyethylene polymer and at least one monomer such as tetrahydrophthalic anhydride. 13. Mixture according to claim 1, characterized in that said carboxylic acid anhydride of component (A) consists essentially of x-methyl-bicyclo (2.2.1) hept-5-ene-2,3-dicarboxylic acid anhydride consists. 14. Mixture according to claim 1, characterized in that said carboxylic acid and the carboxylic acid anhydride of component (A) from x-methyl-bicyclo (2.2.1) hept-5-ene-2,3-dicarboxylic acid and / or its anhydride consists. 15 · Mixture according to claim 1, characterized in that said component (B) consists essentially of an ethylene-hexene (1) -mix polymer resin with a melt index of about 0.26 g / 10 min. And a density of about 0 , 95 g / ccm . 809846/0408 16. The blend of claim 1, characterized in that said component (B) consists essentially of an ethylene-propylene-diene Terpolymerisatharz exists. 17 mixture of claim 1, characterized in that said component (B) is substantially a polyethylene Homopolymerisatharz aue low density having a melt index of about 3.4 g / 10 min. And a density of about 0.935 g / cc is in accordance. 18. Mixture according to claim 1, characterized in that said component (A) consists essentially of an ithylen- butene- (I) copolymer, to the x-methyl-bicyclo ( 2.2.1 ) -hept-5-ene- 2,3-dicarboxylic anhydride and dibutyl maleate have been co-grafted, and component (B) consists essentially of an ethylene-hexene (1 ^ copolymer, 19 · composite material, characterized in that it is made of (A) a solid substrate and one bonded to it (B) modified polyolefin mixture as claimed in claim 1 , consists. 20. The composite material according to claim 19 «characterized in that said substrate consists of a polar polymer! Eat, solid metals, glass, paper, wood, or cellophane. 21 · composite material according to claim 19, characterized in that » that said substrate is made of nylon. 22. Composite material according to claim 19, characterized in that that said substrate consists of aluminum. 272U7A 23. Composite material according to claim 19, characterized in that that said mixture consists of a mixture as claimed in claim 2. 24. Composite material according to claim 19, characterized in that said mixture consists of a mixture as described in Claim 3 is claimed, exists. 25. Composite material according to claim 19, characterized in that said mixture consists of a mixture as described in Claim 4 is claimed, exists. 26. Composite material according to claim 19, characterized in that said mixture consists of a mixture as described in Claim 6 is claimed, exists. 27. Composite material according to claim 19, characterized in that said mixture consists of a mixture as shown in Claim 7 is claimed exists. 28. Composite material according to claim 19, characterized in that said mixture consists of a mixture as shown in Claim 8 is claimed exists. 29. A composite material according to claim 19, characterized in that said mixture consists of a mixture as claimed in claim 9. 30. A composite material according to claim 19, characterized in that said mixture consists of a mixture as claimed in claim 10. 31 Verbundmaterlal according to claim 19, characterized in that said mixture consists of a mixture as claimed in claim 11 · 272U74 - -33 - ic 32. Composite material according to claim 19, characterized in that said mixture consists of a mixture as shown in Claim 12 is claimed, exists. 33. Composite material according to claim 19, characterized in that that the said Geraisch comes from a Geraisch as it is in Claim 13 is claimed, exists. 34. Composite material according to claim 19, characterized in that said mixture consists of a mixture as shown in Claim 14 is claimed, exists. 35. Composite material according to claim 19, characterized in that said mixture consists of a mixture as claimed in claim 15. 36. Composite material according to claim 19, characterized in that said mixture consists of a mixture as claimed in claim 16 . 37. Composite material according to claim 19, characterized in that said mixture consists of a mixture as shown in Claim 17 is claimed exists. 38. Composite material according to claim 19, characterized in that said mixture consists of a mixture as shown in Claim 18 is claimed, exists. Patent attorney 809846/0408