JPS6187740A - Polyolefin blend - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polyolefin blends, particularly particles of a composition consisting of particles of ethylene polymer as a major part and ethylene polymer as a minor part and additives capable of reacting with the polyolefin in the molten state. , wherein such reactive additives may be crosslinkers and/or modifiers, as further defined below.

Polymers of ethylene, such as homopolymers of ethylene and copolymers of ethylene and higher alpha olefins, are used for a variety of end uses, such as as films, fibers, molded or thermoformed articles, pipes, coatings, etc. , used in large quantities.

Polyolefin compositions offered for sale and/or for use in such end-use applications may be used for modification or stabilization of the polymer during processing and/or use of products made from this composition. , often containing reactive and/or non-reactive additives. Typical reactive additives include crosslinking agents and certain unsaturated compounds.

Typical non-reactive additives include antioxidants and other stabilizers, nucleating agents and additives that affect the slipping or blocking properties of the product, or that affect release of the product from the mold used in the processing process. Includes additives that facilitate.

Incorporation of these additives into polyolefin compositions
It is important to do so that the resulting composition has uniform properties.

Polymers are known that have commercially acceptable properties for a variety of end uses. Additionally, improvements in the properties of some polymers may lead to the use of the polymers in improved products and/or new end uses. For example, one method for improving the end-use properties of rotationally molded products from polymers of ethylene is to incorporate crosslinking agents, such as organic peroxides, into the composition of the polymer. In rotational molding of compositions containing organic peroxides, the polymer flows and coats the inside of the mold, and then a crosslinking agent increases the molecular weight of the polymer by causing crosslinking of the polymer, thereby increasing the resulting product. The end-use properties of the material are improved. A crosslinkable composition particularly adapted for rotomolded end use is disclosed in European Patent Publication No. 0087210 to White (G, TI'hite), published Aug. 31, 1983.

It is also possible to use crosslinkable compositions in other end uses to achieve improved product properties. Crosslinking of polymers tends to affect the melt properties of the polymer under low shear rate processing conditions.

An example of the use of partial crosslinking to achieve improved film properties is given in Barbeau Y., published May 18, 1982.
(D. A. Harbourne) Canadian Patent No. 11
No. 23560.

Methods for incorporating additives into polyolefins are known in the art. Non-reactive additives, particularly stabilizers, are often incorporated into the molten polymer during the polymer manufacturing process. Reactive and non-reactive additives can also be incorporated into the polymer by melt blending methods, in which case the additives are injected into the molten polymer as it is extruded into pellets or processed products. or add it in some other way.

When adding additives, it is important to disperse them uniformly throughout the polymer. However, the table shows that for non-reactive additives, the uniformity of additive dispersion is generally less important than for reactive additives. For example, the need for uniformity of dispersion for lubricants or stabilizers
Less important than for crosslinkers. Crosslinking of a polymer increases the molecular weight of the polymer. Therefore, the properties,
In particular, in order to obtain uniform products with properties that depend on molecular weight, it is important to carry out the crosslinking of the polymer in a uniform manner. If the crosslinker is not uniform, the resulting product may have areas of weakness, for example due to either insufficient or excessive crosslinking of the polymer, or gel formation due to excessive crosslinking of the polymer. Particles may form and such gel particles may result in unacceptable appearance and/or weaknesses in the product. In certain processing steps, such as bottle blow molding and sheet and film manufacturing, non-uniform product properties are often more sensitive than in other processes.

In order to obtain a product of uniform quality, the incorporation of reactive additives into the polymer is costly and/or complicated, involving special processing equipment and special extruder screw designs.
Or it was necessary to use a complicated process.

The mixing of organic peroxides and molten polymers is described in Brevolia y (R, S, Gregor), published on May 4, 1965.
i-αn) US Pat. No. 3,182,033 and 1974
It is disclosed in Canadian Patent No. 957,473 to Cook (H.J.), published November 12, 2013.

D, A, Aliα is a U.S. patent issued April 8, 1980, for the blending of crystalline polymers and amorphous nidistomeric polymers for the production of crosslinkable polymers with homogeneous surface acids. No. 4197
It is disclosed in No. 381. The incorporation of reactive additives into polyethylene by physical blending of the polyethylene with different polymers containing the reactive additives is described in the patent application filed concurrently with the present invention, Eoivin (D, W;',
) and ZeLonkα (R9A, ZeLonkα).

Blends of polyolefins have now been found that can be used to incorporate reactive additives into polyolefins in a uniform and economical manner.

The present invention thus provides a polyolefin blend comprising a major portion of particles of a first polyethylene composition and a minor portion of particles of a second polyethylene composition, as a physical mixture. , the first polyethylene is a homopolymer of ethylene and ethylene and at least one Cs.

selected from the group consisting of copolymers of higher alpha olefins, said second polyethylene having at least α8
90. a copolymer of ethylene and at least one Cro 10 higher alpha olefin having a density of f/cd and a melt index in the range of 40 to 200 dy/min, the second polyethylene having a density at least less than that of the first polyethylene. about 0.005 g/csj lower and the melt index of the second polyethylene is at least 1 lower than the melt index of the first polyethylene.
0dy1 minute higher, the composition is a composition of a second polyethylene and a reactive additive selected from the group consisting of crosslinkers and modifiers and mixtures thereof, the reactive additive being in contact with the polyethylene in the molten state. It is something that can react.

In a preferred embodiment of the blend of the invention, the reactive additive is a crosslinking agent that is an organic peroxide.

In another embodiment, the reactive additive is a modifier.

In yet other embodiments, the melt index of the second polyethylene is 40 to sodg 1 minute higher than the melt index of the first polyethylene.

The present invention further provides a polyolefin blend comprising a major portion of particles of a first polyethylene and a minor portion of a normally solid second polyethylene composition as a physical mixture; , the first polyethylene is selected from the group consisting of homopolymers of ethylene and copolymers of ethylene and at least one 04-('10 higher alpha olefin), the second polyethylene has a density of at least 890 y10/i and at least a copolymer of ethylene and at least one C,-(:' the first polyethylene has a shear viscosity not greater than 50 degrees of the shear viscosity of the first polyethylene; In a preferred embodiment, the shear viscosity of the second polyethylene is equal to the shear viscosity of the first polyethylene. The viscosity is not greater than about 30 inches. The present invention further provides a composition comprising, as a physical mixture, a major portion of particles of a first polyolefin and a minor portion of particles of a normally solid second polyolefin composition. A polyolefin blend is provided, wherein the polyolefins are selected from the group consisting of homopolymers and copolymers of hydrocarbon alpha olefins having from 2 to 10 carbon atoms, and the second polyolefin is heated at a temperature of 200°C and a temperature of 400°C. having a shear viscosity not greater than 50 times the shear viscosity of the first polyolefin when measured at a shear rate of 1 second, the composition comprising a second polyolefin, a crosslinker and a modifier, and A composition of reactive additives selected from the group consisting of mixtures, said reactive additives being capable of reacting with said polyolefin in a molten state.

In addition, the present invention provides a polyolefin blend consisting of a major portion of particles of a first polyolefin and a minor portion of particles of a normally solid second polyolefin composition as a physical mixture in a melt processing device. and the second polyolefin is selected from the group consisting of homopolymers and copolymers of hydrocarbon alpha olefins having from 2 to 10 carbon atoms;
The composition has a shear viscosity not greater than 50% of the shear viscosity of the first polyolefin when measured at a temperature of 1°C and a shear rate of 400 seconds, the composition comprising a second polyolefin and a crosslinking agent and a modifier. , and mixtures thereof;
Provided is a method for making a product from a polyolefin and a reactive additive capable of reacting with the polyolefin in the molten state, comprising melting and blending the blend and forming a product from the resulting blend. Totoruru. The present invention also provides methods of making products from the other blends described herein.

The polyolefins of the blends of the present invention are those described herein with respect to such polyolefins, in particular homopolymers of ethylene and/or polyethylene and a relatively small amount of at least one 04""Cs.

Copolymers of higher alpha olefins, such as ethylene with relatively small amounts of butene-1, hexene-1 and/or
or an octene-1 copolymer. however,
It should be understood that polyolefins can be broadly defined as homopolymers or copolymers of hydrocarbon alpha olefins having from 2 to 10 carbon atoms. Methods for producing these polymers are known.

As noted above, the present invention is specifically described as polyolefins being homopolymers and copolymers of ethylene.

The properties of the first polyethylene, such as the density and melt index of the polymer, will depend primarily on the intended end use for the resulting product, but in each embodiment:
Density is approximately o, 890 y/all to approximately 0.970Q
/cd and ASTM D-
The melt index when measured by the method of 1238 (Condition E) can range up to about 100 drt 1 minute. For example, polymers intended for end use as films and sheets tend to have a melt index of less than about 10 dg/min, whereas
Polymers intended for end use as molded articles tend to have higher melt index values. The density and melt index ranges of polyolefins used for various products are well known in the trade.

The properties of the second polyethylene are different from those described above for the first polyethylene. In one embodiment, the density of the second polyethylene is lower than the density of the first polyethylene and is at least α890y/a/i, in particular at least αs i Oct/di, but less than the density of the first polyethylene. At least about o, o o s, especially Q, 008.9/cs! needs to be low. Second, the melt index of the second polyethylene is higher than that of the first polyethylene, 40
~200. Especially in the range of 60 to lsodg 1 minute,
The melt index of the first polyethylene is at least 10 dy/min, preferably at least 20 d/min.
97 minutes needs to be high.

In another embodiment, the second polyethylene has an αs of at least 901/cd, especially at least 0.910j
7/d, a melt index of at least 40 dg/min, and a shear viscosity lower than that of the first polyethylene, in particular a shear viscosity not greater than 50% of that of the first polyethylene. . Preferably, the shear viscosity of the second polyethylene is no greater than 30 inches of the shear viscosity of the first polyethylene. When used in the present invention, the shear viscosity is 400 sec' at 200°C.
Measured at a shear rate of

In a broader aspect of the invention, the second polyolefin has a shear viscosity of 50° of that of the first polyolefin;
In particular, it is not more than 5 to 15% of the first polyolefin.

The second polyolefin is a normally solid polymer and includes a material often referred to as a solid wax;
Materials that are liquid at normal temperature and pressure are not included. The blends of the present invention are physical mixtures and therefore physical separation into their respective components is possible at room temperature.

The second polyethylene contains a reactive additive selected from the group consisting of crosslinkers and modifiers, and mixtures thereof. The expression "reactive additive" as used herein refers to an additive that undergoes a chemical reaction at a temperature at which the polyethylene is in the molten state. However, the rate of the chemical reaction is determined by the temperature of the molten polyethylene. It is not critical, as long as it is substantially above the melting point of the polyethylene. For example, crosslinking agents for polyethylene typically require that the crosslinking reaction occur at or near a temperature above the melting point of the polymer, such as at or near the normal processing temperature. The reaction temperature should be such that adequate mixing of the polymer and its reactive additive can be achieved before extensive reaction between the polymer and its reactive additive occurs. Preferred. The half-life of a crosslinking agent is generally known over a range of temperatures and can be used as an aid in selecting a suitable crosslinking agent for the intended end use. may be a compound or chemical species, in which case a portion of the second polyethylene composition may contain one reactive additive and another portion of the second polyethylene composition. It should be understood that the reactive additive may contain a second reactive additive.Furthermore, the reactive additive may contain a second reactive additive.
species, each of such reactive additives is capable of reacting with the polyethylene in the molten state and/or one of such reactive additives is capable of reacting with the polyethylene in the molten state. It should be understood that one can react with the other.

If the reactive additive is a crosslinking agent, such as an organic peroxide, the first polyethylene may contain the organic peroxide, but this is usually not the case. However, under certain circumstances it may be desirable to incorporate a portion of the crosslinker formulation into the first polyethylene. for example,
As noted in White, supra, if the crosslinkable composition is to include both an organic peroxide and a co-vulcanizing agent, the co-vulcanizing agent is mixed with the first polyethylene and the organic We find it advantageous to mix the peroxide with the second polyethylene. This incorporation of a co-vulcanizing agent into the first polyethylene is believed to aid in the development of a uniform product. In any case, the first polyethylene often contains non-reactive additives known to be incorporated into polyethylene, including antioxidants and other stabilizers, pigments, etc., which are useful in polyethylene. Some of the so-called non-reactive additives may have an adverse effect on cross-linking agents or other reactive additives useful in polyethylene; It should be understood that it is not suitable for use in combination with other agents.

Suitable crosslinkers for blends containing crosslinkers are:
Organic peroxides, especially less(t-alkylberoxyalkyl)benzene, dicumyl peroxide or acetylenic diperoxy compounds. Other organic peroxides are known to those skilled in the art, including t-butyl hydroperoxide and di-t-butyl peroxide. 2.5-Dimethyl-2,5-bis(t-butylperoxyisoglobil)benzene is a suitable organic peroxide and is commercially available from Hercules Inc. under the Parcap trademark. Additionally, the crosslinking agent was 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, which is commercially available from the Lundall branch of Rehapenwald Corporation under the trade name Luversol 130. ing. In one embodiment, the composition of the second polyethylene is similar to the composition disclosed in White, supra, except that the polyethylene is selected to meet the requirements of the present invention. It can be done. Although the amount of crosslinker in the second polyethylene can vary over a wide range, it is preferable to include a high concentration of crosslinker in the second polyethylene and then mix only a small amount of the second polyethylene with the first polyethylene. It seems undesirable to do so. In that case, problems would arise in uniformly mixing the relatively high concentration of crosslinking agent in the second polyethylene into the first polyethylene. When the crosslinking agent is an organic peroxide, it is preferred to have less than 4% by weight of peroxide present in the second polyethylene, preferably from 0.05 to LO% by weight.

As mentioned above, a co-vulcanizing agent can be incorporated into the first or second polyethylene, either separately or mixed with the cross-linking agent. Examples of co-vulcanizing agents are triallyl cyanurate, triallyl isocyanurate and 1.
2-polybutadiene.

Reactive additives may be replaced by modifiers, which may be used alone but are usually used in combination with initiators. Examples of modifiers are unsaturated organic acids and their derivatives, e.g. acids, methacrylic acid, maleic acid, fumaric acid,
Can react with itaconic acid, crotonic acid, maleic anhydride, crosslinking silane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxysilane) and vinylmethyldimethoxysilane, and molten polyethylene. Includes other compounds. The use of sulfur trioxide-trimethylamine complexes as modifiers is described and claimed in a co-pending patent application to RoBoocock, J., filed concurrently with the present invention.

Modifiers are usually used in combination with initiators, especially crosslinking agents, such as organic peroxides. Other initiators are known for certain modifiers;
For example, styrene acts as an initiator for maleic anhydride. The modifier and initiator may be mixed separately in the composition with the second polyethylene. Under certain processing conditions, it may react with polyethylene without the addition of substantial initiator. For example, maleic anhydride and polyethylene are known to react thermally at temperatures of at least about 375°C.

The polyethylene in the blend may contain stabilizers, such as antioxidants or UV stabilizers. Examples of antioxidants are hindered phenolic antioxidants such as octadecyl-3,5-di-t-butyl-4-hydroxycinnamate and tetrakis-methylene-3-(3
', 5'-di monobutyl-4-hydroxyphenyl)
Propionate methane. Hindered phenolic antioxidants are phosphite antioxidants, such as di(stearyl)-pentaerythritol diphosphite, tris-di-t-butylphenyl phosphite, dilaurylthiodipropionate and bis(2, 4-t-
butylphenyl) pentaerythritol phosphite. Examples of UV stabilizers are 2-hydroxy-4-%-octoximinezophenone, 2-(s I-1-butyl-2'-hydroxy-5'
-methylphenyl)-5-chloropenttriazole and Ubis-(2,2cylo,6-tetramethyl-4-biperitedyl)sebacate. Additionally, the polyethylene in the blend may contain lubricants, antiblocking agents, antistatic agents, mold release agents, pigments, nucleating agents or other processing aids, and the like.

Examples of lubricants are erucamide and stearamide, examples of antistatic agents are bis(hydroxyethyl)-tallowamine and glycerin monooleate sb, examples of antiblocking agents are silica and mica, and examples of mold release agents are Calcium stearate and zinc stearate. Examples of nucleating agents or other processing aids include talc, silica, polyethylene glycols, fluorinated distomers, and polyolefin waxes.

As mentioned above, stabilizers or other so-called non-reactive additives can have an adverse effect on cross-linking agents and other reactive additives, and are therefore It is preferred not to use certain combinations of these additives.

The ratio of first polyethylene to second polyethylene can vary over a wide range, particularly from about 5:1 to about 400:1,
In particular, it can vary from about 50:1 to about 100:1. The ratio chosen depends on the amount of reactive additive (or additional reactive additive) incorporated into the blend, the type of reactive additive, the need for a uniform product, and the blend to be produced. It depends on a variety of factors, including the type of processing and the mixing capacity of the equipment used. With regard to the mixing capacity of the equipment, twin-screw ratio machines are more effective than single-screw extruders.

The amount of reactive additive in the blend of the invention depends, inter alia, on the type of reactive additive and the intended end use for the blend. Thus, the amount per million (pptn) in the blend depends on various factors.
It can vary from a few parts to more than 1 percent by weight. Such quantities will be obvious to experts in this field.

If the reactive additive is a crosslinking agent, the first and second polyethylenes are combined in an amount such that the amount of crosslinking agent in the blend ranges from about 25 ppm to about 1000 ppm by weight of the blend. , and mix them. The amount of crosslinker in the blend depends primarily on the intended end use for the blend. Blends intended for the production of highly crosslinked products contain relatively high proportions of crosslinking agent. In contrast, by having small amounts of crosslinking agent present in the blend, only partial crosslinking of the resulting product can be achieved.

The first and second polyethylene particles can be of any convenient shape and size, such as granules, powders, or pellets.

Such a surface form is a commercially available form of polyethylene and/or can be obtained by known methods such as milling, melt pelletizing, etc. However, it is preferred that the particles of the first polyethylene are of substantially the same size as the particles of the second polyethylene composition.

As the size difference between rain particles increases, the tendency for particles of both types to become separated from each other during storage, transportation, or other handling of the blend increases; This is less of a problem when the blend is fed to the extruder immediately after its preparation.

The second polyethylene composition can be manufactured by methods known for incorporating additives into polyethylene. Such methods include melt mixing, coating and extrusion, and injection of additives into molten polyethylene. If the reactive additive is a modifier or especially a crosslinking agent, the reactive additive is incorporated into the polyethylene in such a way that premature reaction with the polyethylene does not occur, as is known in the art. Must.

The blends of the invention can be used to incorporate reactive additives into polyethylene in a particularly flexible and economical manner. The resulting blends can be used in a wide range of end uses, such as those known for polyethylene. Such uses include blow molding methods, film and pipe extrusion methods, sheet thermoforming methods, and rotational molding methods. The equipment used in these methods is referred to herein as melt processing equipment. In a particularly preferred embodiment, the blend is used for the production of films in a blow molding process. As explained below, such use of blends can result in a substantial increase in the production rate of acceptable quality films. However, for any particular combination of equipment, polymer composition, and processing conditions, there is an optimum concentration for the crosslinker, above which increased film production rates adversely affect film quality. There is a risk.

The invention is illustrated by the following examples: Example 1 Parcap R organic peroxide with α55% by weight and 0 by weight
．． A composition of ethylene/butene-1 copolymer containing 55% triallyl isocyanurate was prepared by a melt mixing method. This copolymer is αg5oJil
/CIII and a melt index of 50% g1 min.

This composition has a density of 1lL95511/- and α43dy
Souffle (product name) with a melt index of /min
58A polyethylene was mixed at a polyethylene:composition ratio of 100:1 to provide the blend of the present invention. The blend thus obtained was fed into a blow molding machine equipped with a mold for the production of one gallon bottles. The bottles obtained were of good quality and did not contain gel particles. Other details are shown in the table below as Experiment 1.

For comparison, the density of 0596011/cr/l and 21%
A corresponding composition was prepared containing an ethylene homopolymer having a melt index of gZ and an organic peroxide and triallyl isocyanurate. A blend of this composition and Sflare 58,4 polyethylene (1:10
0) was prepared and supplied to a blow molding machine. This polymer was found to contain pellet-sized gel particles. The polymer melt was unable to fill the mold cavity and the resulting bottles were incomplete and had many holes. Other details are shown in the table below as Experiment 2.

Weight = Y, Chi2) 474 394 493
1) Defined as (width of parison/0.5 x circumference of die orifice)-1 and expressed as a percentage. Measured at 9000 seconds °1 shear in the blow molding process.

2) Actual weight of parison/theoretical weight of parison) -1
and expressed as a percentage. 90 as in l) above
Measured at a shear rate of 00ψ. The theoretical weight of a parison is the weight without the swell and sag.

3)loOI! The time, in seconds, for a parison of weight to hang freely from the die of a blow molding machine.

*Comparative data for the organic peroxide and Sflare 58A polyethylene that does not contain triallyl isocyanurate.

Example 2 A composition of ethylene/butene-1 copolymer containing 0.25% by weight Parcap R organic peroxide and 0.25% by weight triallyl isocyanurate was prepared by a melt mixing method. This copolymer is o,9241/
It had a density of - and a melt index of 53-dg1 min.

This composition was mixed with Sflare 13J4 polyethylene (ethylene/octene-1 copolymer) having a density of 0.93 (1/d) and a melt index of LOdgZ at 50:1.
The blend of the present invention was obtained by mixing the two polyethylene compositions in a ratio of .

The blend thus obtained was fed to a device for the production of films by the blow molding process. The film is 25μ
It had a thickness of m. It has been found that gel-free films can be produced and that the films have a higher melt strength than films made solely from Souffle 374 polyethylene without an organic peroxide composition. . These high melt strengths allowed film production rates to be increased by 40 inches.

Subsequent tests showed that the impact strength and tensile strength of the films were not adversely affected by the use of organic peroxide compositions and/or high production rates.

Example 3 The dynamic rheological properties of the ethylene/butene-1 and ethylene/octene-1 copolymers of Example 2 were measured using a Rheometrics® online rheometer. This rheometer measures the relationship between the complex viscosity coefficient and the angular frequency, which is equivalent to the relationship between shear viscosity and shear rate under linear viscoelastic conditions, according to Melzu-Cox's law. It is.

Dynamic rheological properties were measured at 200° C. under conditions equivalent to a shear rate of 400 seconds 1. The shear viscosities of the ethylene/butene-1 and ethylene/OIf:/-1 copolymers were found to be 980 and 8000 poise, respectively.

As described in Example 2, films of acceptable properties could be made using the above polymers in accordance with the present invention.

Example 4 0.9181! A linear low density polyethylene of the trade name Korun LPX-1 having a density of /- and a melt index of todg/min was extruded as a film using the blown film method. The thickness of the resulting film was 50 μm. The maximum production rate achieved with the equipment and processing conditions used was found to be 38.6 to 9/hour. Production rates are generally limited by, among other things, bubble stability in blown film processes and melt fracture of the polymer at the die lip.

A composition of a melt processing aid and i o o o ppm Rubersol 130 organic peroxide in an ethylene/butene-1 copolymer having a density of 0.92 ON/cd and a melt index of L40 dg/min was added to the polymer at 5% into the linear low density polymer described above to give a composition of When the film was prepared using the method described above, the polymer did not develop a melt 7 lactia. However, the gel content in the film was too high to evaluate the increased stability of the bubbles.

A composition of Rubersol 13G organic peroxide of 2500'I) pfrL in an ethylene/butene-1 copolymer having a density of 0.9241 I/cd and a melt index of 5 sdy1 was used in place of the above composition. It was used at a content of When this blend is extruded as a film, the resulting film is essentially gel-free and the production rate can be increased by 47 times from 5a7 to 9/hour, eliminating melt fracture during operation. It has been found that this does not occur.

Example 5 In a series of experiments, ethylene/alpha olefin copolymer pellets containing Rubersol 130 i peroxide were mixed with Sflare 13F4 polyethylene, i.e.
It was blended with an ethylene/octene-1 copolymer having a density of 0.931'/cd and a melt index of LQ d g1 min.

The blend thus obtained was extruded as a film by the blown film method. The equipment used was equipped with an efficient mixing screw. Additional details about the ethylene/alpha olefin copolymers and the results obtained are shown in Table 1.

Table 1* LQ Chi pellets were used in experiments 1-3 at a weight containing 5000 pptn peroxide; in the remaining experiments 21 pellets were used at a weight containing 5000 pptn peroxide. did.

**Dynamic viscosity measured at 200°C and 400 rad/sec These results indicate that the peroxide containing polymer has a melt viscosity approximately similar to that of the main component polymer. This indicates that a quality film cannot be obtained. The melt viscosity of the peroxide-containing polymer was adjusted to 5 oll of the main component polymer as in Experiments 2 and 5.
Depending on the amount of peroxide used, the quality of the film becomes marginal. However, good quality films are obtained when the melt viscosity of the peroxide-containing polymer is only 20 degrees of the melt viscosity of the main polymer component.

In a related series of experiments, attempts were made to extrude films from a number of blends using equipment with highly inefficient mixing screws.

The melt viscosity of the peroxide-containing polymer is that of the main component Sa
Even when lowered by t, the peroxide concentration had to be less than 2500 pμ to obtain a good quality film. Thus, although the present invention allows the production of films using equipment with highly inefficient mixing screws, the use of more efficient mixing screws is preferred.

Example 6 Approximately 1 s 001 of Sflare 2114 polyethylene, an ethylene/butene-1 copolymer having a density of 92 al/cd and a melt index of 53 dg 1 min, was cleaved using an α48 mesh sieve. It was crushed in the machine. Approximately 45 g of sulfur trioxide-trimethylamine complex was dissolved in 600° C. distilled water at 50° C. and distributed over the polyethylene particles as quickly as possible in a Henschel mixer maintained at 90° C. Ta. Water vapor was removed by continuously passing nitrogen through the mixer for 20 minutes. The coated particles thus obtained were moist and were dried overnight in a vacuum oven at 95°C.

A masterbatch was prepared by extruding the thus dried mixture through a 190 cm single screw Brabender (trade name) extruder equipped with a mixing screw at a melt temperature of 182°C. The extrudate was cooled in a water bath, cut in a strand cutter, and then dried under vacuum overnight.

The calculated amount of sulfur trioxide-trimethylamine complex in the masterbatch was z9th by weight.

23 I masterbatch and 66 (l souffle 11 with polyethylene, i.e. +1920 Ii/d density and L4
A physical mixture of ethylene/butene-1 copolymer with a melt index of 0 dg/min was prepared. This mixture was extruded from a Brabender extruder equipped with an exhaust screw and a breaker plate at a melt temperature of 256°C to form an annotation film having a width of 13.5° and a thickness of 50 μm. Residence time in the extruder was estimated to be 15-5 minutes.

This is how I got it. While the films were dyeable, films from either Sflare 2114 or Sflare IIK polyethylene were rarely dyeable. Moreover, this film showed no sign of significant amounts of black spots that occur when the complex powder is reacted with polyethylene.

The sulfonation of polyethylene using a sulfur trioxide-triethylamine complex was proposed by Boucock (
7, RoB, Boocock).

Example 7 In a series of experiments, pellets of polymer were heated at 250 O
Coated with ppm Rubersol 130 organic peroxide crosslinker. The coated pellets thus obtained are physically mixed at a concentration of 2% with Sflare 13J4 polyethylene, an ethylene/octene-l copolymer having a density of a93GIl/cIi and a melt index of LOdg/min to form the blend of the present invention. gave something. The blend thus obtained was fed to an extruder in a blown film process. This extruder was equipped with the most efficient mixing screw available today.

The obtained films were tested for quality. The results are shown in Table 82.・ (1) Ethylene/butene/octene terpolymer, density 0.910.9/edi melt index L7dy
1 minute (ii) HP PE = high pressure polyethylene, density 0.918 g/-; melt index 7, Od g
7 minutes (ii) Polyethylene wax = polymer of N-34 evolene; density o, 9tOg/ii Brookfield viscosity, 450 centipoise Gv at 125°C) Polypropylene-shell 6300 i density 0
．． 905JF/cj! Melt flow index 2αO
dg/min (V) White concentrate = Tie in high pressure polyethylene.

(vD black concentrate = carbon black in linear low density polyethylene Example 8 ethylene/butene-1 copolymer with a density of α920 g/cd and a melt intex of 1.4 dy1 min,
A physical mixture of the organic peroxide crosslinker concentrate and maleic anhydride was prepared in a Henschel mixer until the mixture was sopped.
It was prepared by containing m of crosslinking agent and 1 by weight of maleic anhydride.

The crosslinker concentrate was in the form of pellets of ethylene/butene-1 copolymer containing Rubersol 130 organic peroxide and having a density of 0.924 g/cm and a melt index of s3 dg/min.

Maleic anhydride was in powder form.

The mixture was mixed in a Henschel mixer at a maximum temperature of about 70° C. for 5 minutes and then extruded through a co-rotating twin screw press ratio. The extruder had a first zone with a temperature of 180°C and a remaining zone with a temperature of 200°C.

A maleic anhydride-grafted polymer containing 0.56-maleic anhydride by weight was obtained. The melt index of the polymer was 0.53.

This graft polymer film is coated with aluminum foil,
Pressed onto nylon, film and ethylene/vinyl alcohol copolymer film at a temperature of about 180°C.

Good adhesion of the graft polymer to the foil or film substrate was observed in all cases.

This example illustrates the use of the present invention with modifiers.

The reaction between maleic anhydride and ethylene/butene-1 copolymer is described in C.N.
, S, rang) and Earl Knee Fist Zelonka (R,
A, Zalonkα), further explained in the patent layer in t[.

Example 9 Ethylene/butene-1 copolymer t2 with a density of α9ss, P/cd and a melt index of 85dg1 min
Blend with sooppm of t-butyl hydroperoxide. The blend thus obtained was physically mixed with pellets of ethylenecybutene-1 fuborimer having a density of α920 p/- and a melt index of 55 df1 in a ratio of 3:97 to 6:9-1.

The mixture thus obtained was fed into a paper extrusion coating rounding process. The extruded mixture had high melt strength such that the speed of the extrusion coating line could be increased from 26 m/min in the absence of the peroxide blend to 46 m/min.

Example 10 An ethylene/butene-l copolymer having a density of o, e241/aII and a melt index of 53d (17 minutes) was blended with 2500 ppWL of Rubersol 13G organic peroxide. −
was physically mixed with Sflare 58A ethylene homopolymer having a density of α960 g/min and a melt index of α43 dg/min. 5 of the obtained blends
It was extruded into a sheet having a thickness of u.

The sheet thus obtained contains gel 1 screa 5
It had higher melt strength and showed improved performance in the thermoforming process than a comparable sheet made from 8A polyethylene.

Example 11 A physical mixture of Sclar tIX ethylene/butene-1 copolymer, organic peroxide and maleic anhydride was prepared having a density of 0.920 g/- and a melt index of tidy 1 min.

Organic peroxide (peroxide concentrate) is Sflare 2114
Polyethylene, that is, (L924N/- density and 5
3d Ethylene/butene-1 copolymer with a melt index of 91 minutes, 4oo.

pptn rubersol 130 organic peroxide and 4000
The composition was in the form of pellets consisting of pμ triallylisocinusate. The maleic anhydride was either in powder form or in the form of a blend in polyethylene as shown below.

This physical mixture was fed into a 19cI11, Prabender single screw extruder and extruded into strands using a melt temperature of 255°C.

Adhesion tests were carried out by pressing the cut strands into a film between aluminum plates at a temperature of 180° C. for about 5 seconds.

Further details and results obtained are given below: Sample
A B -C peroxide concentrate ω) 16,75 111L75
18.75* In Sample A, the maleic anhydride was in powder form; in Sample B, the maleic anhydride was a mixture of maleic anhydride deposited on Sflare 2114 polyethylene ground from the melt in a rotary evaporator. (Concentrate #11 This is about 5% by weight
of maleic anhydride); in sample C, the maleic anhydride was
Grinding souffle 2 by evaporation of the solution at 0-65 °C
114 was in the form of maleic anhydride (
Concentrate #2, which contained approximately 5% maleic anhydride by weight).

** Approximate order of bond strength (l=best) The bond obtained with sample A was very poor.

Claims (1)

Claims: 1. comprising particles of a first polyolefin as a major portion and particles of a normally solid second polyolefin composition as a minor portion, the polyolefins comprising 2 to 1
selected from the group consisting of homopolymers and copolymers of hydrocarbon alpha olefins having 0 carbon atoms, said second polyolefin having the same properties as said first polyolefin when measured at a temperature of 200°C and a shear rate of 400 seconds^-^1. having a shear viscosity not greater than 50% of the shear viscosity of the polyolefin, the composition being a composition of a second polyolefin and a reactive additive selected from the group consisting of crosslinkers and modifiers and mixtures thereof; , the reactive additive is capable of reacting with the polyolefin in the molten state, the polyolefin blend being in a physical mixture. 2. The first and second polyolefins are a homopolymer of ethylene and ethylene and at least one C_4, respectively.
A blend according to claim 1 selected from the group consisting of copolymers of higher alpha-olefins. 3. comprising particles of a first polyethylene as a major portion and particles of a normally solid second polyethylene composition as a minor portion, wherein the first polyethylene is a homopolymer of ethylene and at least 1 type of C
selected from the group consisting of copolymers of C_4~C_1_0 higher alpha-olefins, said second polyethylene having a density of at least 0.890 g/cm^3 and a melt index of at least 40 dg/min and at least one C_4~ C_1_0 high class alpha
a copolymer of olefins, the second polyethylene having a shear viscosity not greater than 50% of the shear viscosity of the first polyethylene when measured at a temperature of 200°C and a shear rate of 400 seconds and the composition is a composition of a second polyethylene and a reactive additive selected from the group consisting of crosslinkers and modifiers and mixtures thereof, the reactive additive reacting with the polyethylene in a molten state. A polyolefin blend in the form of a physical mixture that can be 4. The blend according to claims 1 to 3, wherein the shear viscosity of the second polyethylene is not greater than 30% of the shear viscosity of the first polyethylene. 5. The blend according to claims 1 to 3, wherein the shear viscosity of the second polyolefin is 5 to 15% of the shear viscosity of the first polyolefin. 6. Claim 1, wherein the reactive additive is a crosslinking agent
The blend according to item 5. 7. The reactive additive is a modifier, claim 1
The blend according to item 5. 8. The blend according to claims 1 to 7, wherein the first polyethylene contains a reactive additive. 9. comprising particles of a first polyethylene as a major portion and particles of a composition of a second polyethylene as a minor portion, wherein the first polyethylene comprises a homopolymer of ethylene and a composition of ethylene and at least one C_6 ~C_1
selected from the group consisting of copolymers of _0 higher alpha-olefins, said second polyethylene having a density of at least 0.890 g/cm^3 and a melt index in the range of 40 to 200 dg/min and at least one C_4 ~C_1_0 copolymer of higher alpha-olefins, wherein the second polyethylene has a density at least about 0.005 greater than the density of the first polyethylene.
g/cm^3 and the melt index of the second polyethylene is at least 10 dg/min higher than the melt index of the first polyethylene, and the composition comprises a mixture of the second polyethylene, a crosslinker and a modifier, and mixtures thereof. a composition of a reactive additive selected from the group consisting of: a polyolefin blend in a physical mixture, the reactive additive being capable of reacting with the polyethylene in the molten state; 10. The melt index of the second polyethylene is 20 dg/more than the melt index of the first polyethylene.
10. The blend of claim 9, wherein the blend has a high content. 11. The melt index of the second polyethylene is 40 to 60 higher than the melt index of the first polyethylene.
10. The blend of claim 9, wherein the dg/min is high. 12. The density of the second polyethylene is at least 0.91
The blend according to claims 3 to 11, which has a particle weight of 0 g/cm^3. 13. A blend according to claims 1 to 12, wherein the ratio of first polyethylene to second polyethylene ranges from 10:1 to 100:1. 14. A blend according to claims 1 to 12, wherein the ratio of first polyethylene to second polyethylene ranges from 50:1 to 100:1. 15. The blend according to claims 9 to 11, wherein the density of the second polyethylene is at least 0.008 g/cm^3 lower than the density of the first polyethylene. 16. An apparatus for melt processing a polyolefin blend in a physical mixture comprising particles of a first polyolefin as a major portion and particles of a normally solid second polyolefin composition as a minor portion. supply to,
The polyolefins are selected from the group consisting of homopolymers and copolymers of hydrocarbon alpha-olefins having from 2 to 10 carbon atoms, and the second polyolefin is measured at a temperature of 200° C. and a shear rate of 400 seconds. 50% of the shear viscosity of the first polyolefin when
wherein the composition is a composition of a second polyolefin and a reactive additive selected from the group consisting of a crosslinking agent and a modifier, and mixtures thereof, 1. A method for making a product from a polyolefin and a reactive additive capable of reacting with the polyolefin in the molten state, comprising mixing and forming a product from the blend thus obtained. 17. The first and second polyolefins each contain a homopolymer of ethylene and ethylene and at least one C_
Claim 16 selected from the group consisting of copolymers of higher alpha-olefins from 4 to C_1_0.
The method described in section. 18. An apparatus for melt processing a polyolefin blend in a physical mixture comprising particles of a first polyethylene composition as a major portion and particles of a normally solid second polyethylene composition as a minor portion. wherein the first polyethylene is selected from the group consisting of homopolymers of ethylene and copolymers of ethylene and at least one C_4 to C_1^0 higher alpha-olefin, and the second polyethylene is provided with at least 0.890 g/
ethylene and at least one C_4~ having a density of cm^3 and a melt index of at least 40 dg/min
C_1_0 is a copolymer of higher alpha-olefins, the second polyethylene having a shear viscosity not greater than 50% of the shear viscosity of the first polyethylene when measured at a temperature of 200°C and a shear rate of 400 seconds^-^1. the composition having a shear viscosity, the composition being a composition of a second polyethylene and a reactive additive selected from the group consisting of a crosslinking agent and a modifier, and mixtures thereof; A method of manufacturing a product from a polyolefin and a reactive additive capable of reacting with the polyolefin in the molten state, comprising forming the product from the blend thus obtained. 19. The method of claims 16-18, wherein the shear viscosity of the second polyethylene is not greater than 30% of the shear viscosity of the first polyethylene. 20. Claims 16 to 18, wherein the shear viscosity of the second polyethylene is 5 to 15% of that of the first polyethylene.
The method described in section. 21. The density of the second polyethylene is at least 0.91
21. The method according to claims 18 to 20, which is 0 g/cm^3. 22. feeding a polyolefin blend in a physical mixture comprising particles of a first polyethylene composition as a major portion and particles of a composition of a second polyethylene as a minor portion; Here, the first polyethylene is at least one of an ethylene homopolymer and ethylene. selected from the group consisting of copolymers of C_4 to C_1_0 higher alpha-olefins, said second polyethylene having a density of at least 0.890 g/cm^3 and from 40 to
a copolymer of ethylene and at least one C_4 to C_1_0 higher alpha-olefin having a melt index in the range of 200 dg/min, the second polyethylene having a density of at least about 0.005 g/min less than the density of the first polyethylene; cm^3 lower, and the melt index of the second polyethylene is at least 10 dg/min higher than the melt index of the first polyethylene, and the composition comprises the second polyethylene, a crosslinker and a modifier, and mixtures thereof. a composition of reactive additives selected from the group consisting of: reacting with a polyolefin and the polyolefin in the molten state, the composition comprising: melting and mixing the blend and forming a product from the blend thus obtained; A method of manufacturing products from reactive additives that can be used. 23. The method according to claims 16 to 22, wherein the reactive additive is a crosslinking agent. 24. The method according to claims 16 to 22, wherein the reactive additive is a modifier. 25. The method of claims 16-24, wherein the ratio of first polyolefin to second polyolefin ranges from 10:1 to 100:1. 26. The method of claims 16-25, wherein the rate of extrusion of the polyolefin to form the product is higher than the rate for extrusion of the same polyolefin in the absence of reactive additives. 27. The method of claim 26, wherein the method is a blown film extrusion method.