JPH0543753A - Blend of polypropylene with polar polymer - Google Patents

Abstract

PURPOSE: To provide the title blend comprising a polar polymer, polypropylene and a specific compatibilizing agent and excellent in dispersion stability and impact strength.

CONSTITUTION: The objective polymer blend consists of 100 pts. of polypropylene (A), 10-175 pts. of a polar polymer (B) and 3-35 pts. of a compatibilizing agent (C) and is characterized by that the component C comprises a segmented copolymer consisting of the first segment of the component A and a second segment derived from 80% or more of a methacrylate monomer (i) and below 20% of an acrylic or styrenic monomer copolymerizable with the methacrylate monomer (ii).

COPYRIGHT: (C)1993,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION Polypropylene has many attractive features, including its low cost, its chemical resistance and its low specific gravity. Despite these characteristics, polypropylene has some limited use due to its drawbacks to compete in some markets.

Their disadvantages are low rigidity at room and high temperatures, poor resistance to abrasion and scratching, low resistance to aliphatic hydrocarbon solvents, high mold shrinkage, low flame resistance and poor adhesion to polar substrates.

If the polar polymer is compatible with polypropylene, blending with the polar polymer can overcome many of these disadvantages. Compatibility means that the blend is the average of the physical and chemical properties of the ingredients, or the physical properties in which the best properties of both, such as improved service temperature while retaining good chemical resistance, are exhibited. And that it can be processed into something useful with chemical properties. However, most polypropylene blends with polar polymers are incompatible and the blends are weak, cheese-like or brittle, or difficult to mold.

[0004]

Many incompatible polymer blends can be made compatible by the presence of polymer compatibilizers, with small amounts of the above compatibilizers being free of compatibilizers. It results in improved blend properties compared to the same blend.

[0005]

The inventor has discovered a very useful compatibilizer for polypropylene blends with polar polymers, which compatibilizers include polymeric and non-polymeric compatibilizers.
It is further useful when the blend contains various additional components. The compatibilizer is a segmented copolymer of polyolefin and polymethacrylate, as described in more detail below in the text and examples.

As used herein, polypropylene includes isotactic polypropylene, as well as random and block copolymers with up to 25% ethylene. Also up to 40% of other polyolefins such as polyethylene, ethylene-propylene copolymer rubber and E
PDM is also included.

Suitable polar polymers exhibiting improved properties which when blended with polypropylene eliminate one or more of the above mentioned disadvantages include acrylonitrile-butadiene-styrene copolymers, acetal polymers, polyacrylates, Acrylic-styrene copolymer, acrylonitrile-styrene-acrylic copolymer, acrylonitrile-styrene polymer modified by ethylene-propylene rubber, cellulosic material, polyester-
Polyether block copolymer, polybutylene terephthalate, polyethylene, etc., polyester including liquid crystalline polyester, polyether amide, polyether ether ketone, polyether imide, polyether sulfone, ethylene-vinyl alcohol copolymer, polyvinyl chloride , Chlorinated polyvinyl chloride, polyvinyl chloride and vinylidene fluoride, styrene polymers such as polystyrene, high impact polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride (SMA) copolymer , Styrene alone or styrene and acrylonitrile, alkyl-substituted styrene copolymerized with butadiene or maleic anhydride, polyphenylene ether, polyphenylene sulfide, polysulfone, polyureta , Polyamides such as nylon 6,
Nylon 6,6, Nylon 6,9, Nylon 6,10, Nylon 6,12, Nylon 11 and Nylon 12, Amorphous Nylon, Polyamideimide, Polycaprolactone,
Polyglutarimide, poly (methyl methacrylate), other C ₁ -C ₈ poly (alkyl (meth) acrylate), as well as polycarbonate.

Blends of two or more of these also form polar polymer moieties. Examples of suitable pairs are polycarbonate-ABS, polyester-polycarbonate, PVC-polyglutarimide, PVC-ABS, polycarbonate-polyamide, ABS-polyglutarimide, ABS-SMA, ABS-polyamide, ABS-.
PMMA, polycarbonate-poly (meth) acrylate, polycarbonate-SMA, ABS-polysulfone, PVC-polyamide, PET-PBT, PET-polyglutarimide, PET-PPO, PBT-PPO,
PBT-polyglutarimide, polyamide-polyglutarimide, polyamide-PPO, polystyrene-PPO
And polystyrene-SMA.

The amount of polar polymer required in the blend depends on the polar polymer used, the effect on the property of interest and the application. Generally, a minimum of 10 parts polar polymer (based on 100 parts polypropylene) can be used to obtain a significant effect, but from about 10 parts to about 1 part.
75 parts may be used. The amount of polar polymer used should be kept below specified limits in order to preserve the polypropylene nature of the blend. If the capacity of the polar polymer phase is less than the capacity of the polypropylene phase of the blend, generally the specified limits are not exceeded. In the case of polymers such as ABS this occurs at about 110 parts per 100 parts polypropylene. In the case of high density polymers such as PVC, this occurs at about 175 parts. All parts are parts by weight.

The function of the segment type copolymer compatibilizing agent such as a graft copolymer is to compatibilize the polar polymer with polypropylene. Without a segmented copolymer, such as a graft copolymer, the blend is cheese-like,
Shows low strength. In some cases, the copolymer compatibilizer is
It also contributes to the performance of the blend by increasing the efficiency of the polar polymer or by contributing to the beneficial effects of the polar polymer.

Compatibilizing polymers include polyethylene, polypropylene, polybutylene, poly (4-methylpentene),
Copolymers of the olefin with others, as well as small amounts of 1
At least one first segment selected from the group consisting of one or more copolymers of said olefin with alkenes, vinyl esters, vinyl chloride, (meth) acrylic esters and (meth) acrylic acid; And the formula CH
₂ ═C (CH ₃ ) COOR (wherein R is alkyl, aryl,
At least 80 monomers which are methacrylic esters of substituted alkyl, substituted aryl or cycloalkyl)
% And at least one second segment covalently bonded to the first segment derived from less than about 20% of an acrylic or styrene monomer copolymerizable with the methacrylic ester. It is a copolymer. The term "segmented copolymer" is meant to include both graft and block copolymers.

The molecular weight of the polyolefin segment is preferably from about 50,000 to about 1,000,000 MWw.
(Weight average molecular weight). The molecular weight of the polymethacrylic acid ester segment is preferably from about 20,000 (weight average molecular weight) to about 200,000. The ratio of polyolefin segment to poly (methacrylic acid ester) is preferably from about 9: 1 to about 1: 4.

Suitable graft copolymers are described in US Pat.
957,974. Preferably, the trunk is a homopolymer of polypropylene,
A graft copolymer in which the graft is a polymer of at least 80% methyl methacrylate. A block copolymer having a similar structure can also be used.

Suitable graft copolymers are described in US Pat.
957,974, and a monomer mixture containing at least 80% methyl methacrylate was controlled to obtain a particular radical flux controlling the molecular weight of the polymethacrylate. Polymerization is carried out in the presence of a polyolefin such as polypropylene in a solution or slurry process with a free radical initiator added under conditions. Suitable block copolymers can be prepared by methods such as hydrogenation of block copolymers prepared by sequential anionic polymerization of isoprene and methyl methacrylate.

The amount of segmented compatibilizer present in the blend may vary from about 3 to about 35 parts based on 100 parts polypropylene.

Further additives are required for commercial success in most polymers, especially for use as "industrial resins". Additives are used to improve the chemical properties of the blend, such as resistance to oxidation, heat, solvents, light, etc. Other applications were improved processing, such as improved flowability, overcoming adhesion to hot metal surfaces, improved thermoforming, etc. A third use of the additive is to improve the physical properties of the blend, such as improved thermal deformation, increased modulus, toughening, etc. The above additives are often used separately for polypropylene or polar polymers.

The addition of other ingredients has advantages in many of these applications. The above additives are impact resistance imparting agents, fillers, reinforcing agents, antioxidants, heat stabilizers, ultraviolet (UV) stabilizers, antistatic agents, flame retardants and synergists, plasticizers, lubricants. Agents, release agents, and colorants are included. Of course, the presence of these materials is optional, as different additives are used if desired.

The amount of additive used for various purposes will vary depending on the desired results, but generally the level of use will be
Optionally up to about 5 parts of an additive which is at least one of antioxidants, anti-ozone agents, UV stabilizers, antistatic agents, colorants, lubricants or processing aids, and optionally The additive is at least one of from about 5 to about 200 parts (phr) or more of impact modifier, reinforcing filler, non-reinforcing filler, flame retardant or plasticizer. Impact modifiers are rarely needed at levels above 80 phr, usually below 40 phr.

The segmented polyolefin / polymethacrylate compatibilizer of the present invention comprises a polymer additive, particularly a dispersion of impact modifier within the polypropylene component of the blend,
It is also useful in promoting even distribution.

Impact modifiers may be added to improve the impact strength of the blend. The impact modifier can act in the polypropylene phase, the polar phase, both phases, or at the interface. Examples of impact modifiers are MBS core-shell modifiers, all acrylic core-shell modifiers, butadiene-styrene random and block copolymers, acid modified butadiene-styrene copolymers, ethylene-propylene. (EP) Copolymer rubber, ethylene-
Propylene-diene terpolymer, acid modified EP, acid modified E
Includes PDM, polyethylene, chlorinated polyethylene, acrylonitrile-butadiene rubber, ionomers, and ethylene-vinyl acetate copolymers.

Fillers and tougheners are often used with the polymers described above and can be beneficially incorporated into the blend. Among the suitable fillers and reinforcing agents are solid glass beads, calcium carbonate, wood flour, clay, alumina,
Mica, aluminum silicate, carbon black, hollow glass and ceramic spheres, calcium silicate, eg Wollasto
nite, metal flakes and fibers, flake, glass fiber,
Polymer fibers as well as carbon fibers are wrapped.

In general, polar polymers improve flame resistance, but additional flame retardant compounds can be added to further improve. Suitable flame retardants and synergists include phosphate esters, brominated aromatics such as decabromodiphenyl oxide, antimony trioxide, hydrated alumina, ammonium polyphosphate, molybdenum trioxide, chlorinated alkanes and cycloalkanes, and boric acid. Includes zinc.

Blowing agents may also be used advantageously in these blends, especially in applications where light weight, strength or insulation are important. Suitable blowing agents include gases such as nitrogen and carbon dioxide, and chemical blowing agents such as azodicarbonamide, azoisobutyronitrile, hydrazo compounds and compounds containing nitroso groups.

Stabilizers may be required to stabilize the polymer during high temperature processing, prolonged use at elevated temperatures, or during exposure to light. Antioxidants such as sterically hindered phenolics and secondary aromatic amines are
The chain decomposition mechanism is stopped by stopping the radicals, which are used. Sulfur or phosphorus containing compounds are used and stabilized by decomposing any peroxides that may be present. Thioesters and phosphites are typical examples. Compounds based on lead, cadmium and tin are important for the stability of PVC.
Benzophenone, benzotriazole and sterically hindered amines are important for preventing photoinduced degradation. Plasticizers such as phthalates, azipates, glutarates,
Azelates, phosphates, trimellitates and sebacates are important additives when improved flexibility is required.

Additives are also important during processing to ensure that the molten polymer does not stick to the metal surface and flows well. These lubricants or mold release agents are often fatty acids or their esters, amides or metal salts. Paraffin, silicone and fluorocarbon polymers are also often used.

When special parts have to be colored, additional additives can be colored internally. Dyes such as carbon black and azo dyes and anthraquinones, inorganic pigments, and organic pigments are used.

The polymer compatibilizer is used to introduce carboxyl, hydroxyl, epoxide and other functionalities.
It may be functionalized by using certain functional monomers in the grafting operation. The above functionality may be useful in improving the printability or paintability of treated articles from the blends.

Rigidity One of the drawbacks of polypropylene is its low rigidity. This is especially true for impact grade polypropylene copolymerized with propylene or blended with ethylene in the form of added polyethylene or ethylene-propylene polymer. This low rigidity means that polypropylene cannot carry a large load. When polypropylene is used in load bearing applications, it requires additional supports (shorter beams) or thicker cross sections.

The stiffness or modulus of a polymer is measured by tensile or bending tests. The elastic modulus of polypropylene can be increased by the addition of polar polymers. The increase in elastic modulus approximates that predicted by the weight average performance of the components. Blend elastic modulus = PP elastic modulus × PP weight fraction + polar polymer elastic modulus × polar polymer weight fraction Therefore, in order to increase the elastic modulus of the blend,
High modulus polar polymers are preferred and the highest modulus is
Achieved in blends with the highest modulus polar polymers. Particularly suitable are polyglutarimides,
PMMA, SAN, acetal, polyphenylene sulfide, polyamide, polyether sulfone, polycarbonate, polysulfone, PVC, and polycarbonate and poly (meth) acrylate, polycarbonate and SMA, PVC and polyglutarimide, polyester and PPO, polyester and polyglutarimide,
Polyamide and PPO, and polystyrene and PPO
Is a blend of.

Based on 100 parts of polypropylene, 25 to 175 parts of polar polymer are required to achieve this effect. In some cases 25 parts is sufficient for the desired increase. When it is necessary to preserve the polypropylene nature of the blend, additions in amounts exceeding 130-175 parts (depending on the polar polymer) should be avoided.

The purpose of the segmented copolymer compatibilizer in these formulations is to compatibilize the blends. That is, to provide sufficient adhesion between the polypropylene and polar polymer phases to minimize delamination. In some cases, the compatibilizer also contributes to further improving the elastic modulus. About 5 to about 20 phr of segmented copolymer is generally sufficient to provide additional adhesion, but higher amounts are sometimes beneficial.

Some of the additional additives are also useful in increasing modulus. Fibrous reinforcing agents (eg glass) and additives such as talc and calcium carbonate are specifically mentioned.

The additives mentioned above, due to their increased stability,
It can be included either for color, for impact strength, or for other benefits it provides.

There are several applications of polypropylene that would benefit from increased stiffness. Profitable automotive applications include under-the-hood parts such as fan shrouds, air cleaner housings, engine shields,
And steering column assemblies, interior parts such as instrument panel consoles, instrument bezels and window and door handles, and exterior parts such as lamp housings, mirror housings, wheel covers, bumper reinforcements, fenders and body plates. Other applications are bearing cages, power equipment housings, ski bindings, gears, rollers, slides and cams.

Strength Polypropylene has a relatively low strength. Polypropylene breaks under moderate loads. Tensile strength is a measure of the force required to break a plastic part. When the blend is compatibilized with, for example, a polyolefin-acrylic graft copolymer,
The addition of high strength polar polymer increases this tensile strength. Almost all polar polymers are stronger than polypropylene and almost all can increase the strength of polypropylene when properly compatibilized.
Examples of the polar polymer include polyglutarimide, polycarbonate, polysulfone, polyamide, polyphenylene sulfide, poly (meth) acrylate, acetal,
And blends of polycarbonate and ABS, polyglutarimide and PVC, polycarbonate and polyester, and polyamide and polyglutarimide.

Based on 100 parts of polypropylene, about 2
5 to about 150 parts of polar polymer increase the tensile strength of the polypropylene without destroying the nature of the blended polypropylene.

The segment type copolymer compatibilizer is necessary for the tensile strength of the polar polymer to contribute to polypropylene. That is, to provide sufficient adhesion between the polypropylene and polar polymer phases to minimize delamination. Without the compatibilizer, the tensile strength of the blend drops well below the weight average value. About 5 to about 20 phr of a segmented copolymer, such as a graft or block copolymer, is generally sufficient to provide additional adhesion, but larger amounts are sometimes beneficial.

The additional additives mentioned above can also be included either for increased stability, for color, for impact strength, or for any other benefit they provide.

There are several applications of polypropylene that would benefit from the increased strength of polypropylene-polar polymer blends. Profitable automotive applications include under-the-hood parts such as fan shrouds, air cleaner housings, engine shield and steering column assemblies, interior parts such as instrument panel consoles, instrument bezels, and window and door handles, and It includes exterior parts such as lamp housings, mirror housings, wheel covers, bumper reinforcements, fenders and body plates. Other applications are bearing cages, power equipment housings, ski bindings, gears, rollers, slides and cams.

Rigidity at high temperature Polypropylene has low rigidity even at high temperature.
This limits polypropylene's ability to carry loads at elevated temperatures. This is especially true for heavy loads. This characteristic is that the elastic modulus (Clash-Ba
rg torsional modulus) or load (264 psi)
Or 66psi) which causes the deflection (DTUF
L) is measured.

DTUFL can be increased by the addition of polar polymers. This increase is actually higher than predicted by the weight average composition. Suitable polar polymers have high DTUFL or polypropylene D
It has a high elastic modulus in the TUFL temperature region. Polyglutarimide, polyphenylene sulfide,
Polysulfone, polyaryl ether, polyether sulfone, acetal, polyamide, polycarbonate,
Included are PBT, DET and polycarbonates and polyesters, polycarbonates and polyamides, ABS and polyglutarimides, DET and PBT, polyesters and polyglutarimides, polyesters and PPOs, and polyamides and polyglutarimides.

Based on 100 parts of polypropylene, the amount of polar polymer which achieves these effects is about 2 parts of polar polymer.
It should be from 0 to about 150 parts. 20 in some cases
Parts are sufficient for these changes. 120-150
Additions in excess of parts (due to polar polymers) should be avoided when it is necessary to preserve the polypropylene nature of the blend.

The purpose of the segmented copolymers described above in these formulations is to compatibilize the blends. That is, it does not contribute significantly to the DTUFL or high temperature modulus, but rather provides sufficient adhesion between the polypropylene and polar polymer phases to minimize delamination. About 5 to about 20 phr of graft copolymer is generally sufficient to provide additional adhesion.

Some of the additional additives also help in increasing DTUFL. Polymer HD if specified
T improvers such as polyglutarimide, SMA and alpha-methylstyrene copolymers, fibrous reinforcing agents such as glass, and fillers such as talc and calcium carbonate.

Other additives may be incorporated as appropriate for the application. Included are antioxidants and stabilizers, impact modifiers, and colorants.

There are several applications of polypropylene that would benefit from increased DTUFL. Under-the-hood automotive components, housings and components for power equipment and equipment, cooking utensils, microwaves, iron and toaster handles, hot water heaters and air cleaners.

Resistance to Aliphatic Hydrocarbons The chemical resistance of polypropylene in general is very good. However, it lacks good chemical resistance to aliphatic solvents. This type of solvent includes gasoline, kerosene and oil. The effect of this is that the time and temperature during which the contact with the aliphatic hydrocarbon is present can lead to swelling and discoloration to deformation, and to either extraction or solubilization.

The polar polymer is effective in blocking the effect of the solvent on polypropylene. Polyphenylene sulfide, PVC, polyglutarimide, acrylic materials, polyacetal, polyamide, polyester, SA
Blends of N and PVC and polyglutarimides, polyamides and polyglutarimides, and polyesters and polyglutarimides are particularly effective.

The amount required for this effect depends on the application and the conditions. For mild conditions requiring only a small effect, a small amount of 25 parts is effective. For more severe conditions, large quantities of 125-175 parts (depending on polar polymer) may be required.

Among the segment type copolymer compatibilizers are:
It may contribute a little to the resistance of aliphatic hydrocarbons, but its main function is to compatibilize polar polymers and polypropylene. The amount required is in the range of about 5 to about 35 phr based on polypropylene.

Applications in which this effect is desirable include fuel caps, level sensors, floats, pumps, fuel handling systems for hoses, fuel vapor canisters and tubing, fuel storage containers such as gasoline cans, underground tanks and gasoline tanks. And parts having surfaces that become exposed to fuel by accidental contact, such as fuel filler doors, body plates, motor housings, valve covers, distributor caps, rotors, valve covers, lawn mower housings, tractor parts, Includes power equipment housing and oilfield hardware.

Flame resistance Polypropylene also burns quickly and easily, making it difficult to make it flame resistant with additives. It can be measured by the rate of diffusion of the flame, the time it takes for the flame to extinguish itself, or the amount of oxygen required to support combustion (oxygen coefficient).

Some polar polymers serve to improve the flame resistance of polypropylene. Of particular interest are those with aliphatic chlorine or aromatic bromine known to improve flammability, such as PVC, CPE, C.
PVC, brominated polycarbonate, and PVC and C
PE and a blend of PVC and CPVC. However, other polymers with inherently good flame resistance can be used to improve the flame resistance of polypropylene. In these cases it is almost certain that additional flame retardant material will be required. Examples are polypropylene sulphide, polycarbonates, polyesters, polysulfones, and polycarbonates and ABSs, polycarbonates and polyesters, ABSs and PVCs, PVCs and polyglutarimides, PETs and PBTs, and polyesters and PPOs.
Is included.

The amount of polar polymer required depends on the degree of flame resistance required. A small amount of 40 phr is beneficial. 125-175 phr for most demanding conditions
A large amount of may be used.

A segmented copolymer compatibilizer, such as a graft copolymer, is necessary for structural integrity.
Besides, it results in a finer dispersion of the polymer and thus better fire resistance.

As noted above, for some applications some of these formulations may require additional flame resistant additives. In addition, some applications may require additional additives. These types of applications benefit from the addition of antioxidants and heat stabilizers, fillers and tougheners, impact modifiers, and colorants.

Applications that would benefit from the increased flame resistance of polypropylene are power appliance housings, siding, construction materials, and electrical components and connectors.

Mold Shrinkage Polypropylene as a crystalline polymer undergoes excessive shrinkage when molded. This is because crystallization increases the density. The effect of this is that the dimensions of the mold do not fit well and that there is poor reproduction during automatic cutting and cutting. Molding strains can distort parts if their external shrinkage is severe and / or anisotropic. This is important in all processing techniques including cooling from the melt, such as injection molding, thermoforming, blow molding, and sheet and profile extrusion.

The polar polymer reduces the shrinkage of polypropylene. Particularly suitable are polymers which can be compatibilized by segmented copolymers, such as block or graft copolymers, and which themselves cool and do not shrink significantly. Polyglutarimide, acrylic polymer, polyphenylene sulfide, PPO, polyether sulfone, polycarbonate, ABS, SAN, polysulfone, PVC, and polycarbonate and ABS, polycarbonate as polar polymer capable of reducing the shrinkage of polypropylene in processing technology And poly (meth) acrylates, ABS and PVC, ABS and polyglutarimide, PVC and polyglutarimide,
And polystyrene and PPO blends.

The amount required depends on the amount of shrinkage. Small amounts of 10 phr produce some reduction. However, for significant reduction, 40 parts or more are generally used. Use of amounts in excess of 120-175 parts (depending on polar polymer) can destroy the properties of the blended polypropylene. About 4 to about 25 parts of the graft copolymer can be used to compatibilize the polar polymer with polypropylene for use in reducing shrinkage.

Applications in polypropylene that would benefit from reduced shrinkage or molding strain include electronics assemblies, plastics lumbars, precision equipment and body plates. All injection molded parts benefit.

Adhesion Polypropylene itself is very non-polar and hydrophobic and the surface interacts poorly with polar substrates and with itself. This means that it is difficult to coat polypropylene parts with water-based paint, laminate polypropylene parts with other polypropylene parts, metal parts or fabrics, bond them to paper, labels, etc. means.

The addition of highly hydrophilic or ionic polymers increases the ability of polypropylene to interact with these substrates. Suitable polymers that produce these effects when incorporated in polypropylene are polyacrylic acid,
Polyethylene oxide, ionic forms of polyacids, and polyamines and polyamine salts.

In order to increase the polarity of the surface sufficiently for interaction with polar substrates, it is generally about 10 to about 50 phr.
Of polar polymers are used. These levels of polar polymer have the further advantage of reducing the electrostatic charge generated in polypropylene.

About 3 to about 15 parts of the graft copolymer is generally used to compatibilize the polypropylene with the polar polymer. When the graft or block copolymer contains hydrophilic or acidic functionalities such as carboxylic, neutralizing carboxylic, hydroxyl, etc., it further increases adhesion to polar substrates.

Applications which require increased adhesion to paint, such as bumpers and bumper covers, instrument panels,
In the case of car body plates, outer door components, and window frames, application including adhesion of metal to equipment panels and multilayer components, equipment panels,
Applications including bonding to textiles such as insulation panels and door panels,
And applications including gluing to water-based inks such as bread bags, grocery sacks and containers.

Mer resistance polypropylene is a relatively soft material and its surface is easily scratched. Not only does this affect appearance, but it can also initiate catastrophic outages of parts. This mar resistance or hardness can be measured by a standard hardness test (Rockwell) or by an abrasion test (Taber).

The polar polymer in combination with the graft copolymer increases the hardness. The polar polymer itself actually reduces the hardness of polypropylene due to the incompatibility of the polar polymer and the propylene polymer. However, compatibilization by graft or block copolymerization increases hardness to values above that of polypropylene alone. Suitable polar polymers include polyglutarimide, polymethacrylate,
Acetal, aromatic polyamide, polyphenylene sulfide, polyether sulfone, polycarbonate, PB
T, SAN, PVC, and polyglutarimide and P
Includes VC, polycarbonate and poly (meth) acrylate, as well as polyglutarimide and SAN.

The amount of polar polymer that can be used is
It is about 20 to about 175 phr. About 3 to about 25 parts of the graft or block copolymer is sufficient to compatibilize the polar polymer with the polypropylene and blend the polar polymer with the polypropylene to overcome the loss of hardness that is exceeded.

The applications are hard interior applications for automobiles, ABC mirrors,
Includes decorative moldings and bumpers (unpainted or tinted).

[0071]

EXAMPLES In the following examples and tables, the polypropylene and polar polymers used in the examples and the abbreviations used for each polar polymer are as follows:

[0072]

[Table 1]

Example 1 This example illustrates the effectiveness of some compatibilizers of the present invention as compatibilizers for polypropylene and polar polymers that have poor compatibility without compatibilization. To do. Table 1 above summarizes the polymers used in this example. Table 2 demonstrates the tensile strength of the blended polymers in the presence of the compatibilizer, which increases the compatibility of the blended polymers with each other in the presence of the graft copolymer of the present invention. Indicates that.

The blend had a screw length to diameter of 10:
Produced by compounding at 200 rpm in a screw interlocking co-rotating twin screw extruder with 1. The temperature was adjusted to the composition for the various blends and to produce a processable melt.
The melt was fed directly into a 38 mm single screw pellet extruder with a length to diameter of 8: 1. Next, these strips were injection-molded into samples for obtaining tensile strength. The compatibilizer is as described in Example 52 of U.S. Pat. No. 4,957,974,
Graft copolymer of methyl methacrylate / ethyl acrylate (95/5) copolymer on polypropylene (mfr = 4), containing about 40% polypropylene.

[0075]

[Table 2]

[0076]

[Table 3]

Example 2 This Example 2 further illustrates compatibilization of a polymer blend using a polypropylene // methyl methacrylate graft copolymer as a compatibilizer. Ethylene-vinyl alcohol copolymer (Kuraray E
P-F101A), polypropylene (Himont 6523) and graft copolymer 204 on an electric mill of 7.62 cm x 17.78 cm.
Triturated at ℃ and melted for 3 minutes. This stock was stored at 204 ° C and 103 MPa for 3 minutes (Carver Pr
ess, 12.7 cm x 12.7 cm x 3.175 mm mold) and pressed at room temperature and 103 MPa for 3 minutes. Two graft copolymers were used in this example. The first (Graft Copolymer A) is prepared from polypropylene homopolymer of mfr = 4 (100 parts) and a 93: 2: 5 mixture of methyl methacrylate: ethyl acrylate: methacrylic acid (100 parts). It was a polypropylene-acrylic graft copolymer. Polymerization at 160 ° C
Performed at 50% solids in Isopar E solvent for 1 hour with 0.0012 di-t-butyl peroxide radical flux. 44% isolated product
Of acrylate. The second graft copolymer (graft copolymer B) is a polypropylene produced from a preprene homopolymer of mfr = 4 (100 parts) and a 95: 5 mixture of methyl methacrylate: ethyl acrylate (150 parts). It was an acrylic graft copolymer. The polymerization was carried out at a fixed content of 60% in Isopar E solvent at 155 ° C. The supply time was 60 minutes, and the radical flux was 0.00010. 5 products
It contained 3% acrylate. The addition of the graft copolymer results in an increase in tensile strength and elastic modulus.

[0078]

[Table 4]

Example 3 This example demonstrates the increase in modulus at 23 ° C. and 80 ° C. caused by the addition of poly (methyl methacrylate) (PMMA) polymer to polypropylene. It also demonstrates the need for polypropylene / polymethacrylate graft copolymers as compatibilizers (tensile strength).

Polypropylene homopolymer (Himont Pro F
ax 6523, PP in Table 5), acrylic polymer (Rohm and
A blend of Haas Plexiglas VM) and the graft copolymer compatibilizer (B) of Example 2 was prepared in a co-rotating extruder and melt extruded into a single screw extrusion pelletizer. This blend was injection molded and tested.

[0081]

[Table 5]

Example 4 This example illustrates the effect of ABS on polypropylene stiffness and 264 psi DTUFL at 23 ° C. It also demonstrates the effect of compatibilizers.

ABS (General Electric Cycolac DFA-
R) and polypropylene (Himont ProFax 6823) were compatibilized with the graft copolymer (B) described in the examples by compounding in a co-rotating twin screw extruder.
This blend was injection molded and tested.

[0084]

[Table 6]

Example 5 This experiment demonstrates the effect of ABS on mold shrinkage of polypropylene. The polypropylene / ABS / polymethacrylate graft copolymer used was (B) in Example 2. The lengths of the injection molded parts were measured before and after annealing. The lengths of the parts demonstrate that polypropylene / ABS blends with compositions between 0/100 and 70/30 are more ABS like than polypropylene like in mold shrinkage.

[0086]

[Table 7]

Example 6 This example shows the rigidity of polypropylene copolymer, DTU of 264 psi (1820 kPa).
3 illustrates the effect of PVC on FL and hardness.

A PVC masterbatch was prepared. K = 6
50 pounds of 0 PVC and TM181 organotin stabilizer were mixed at room temperature. When the temperature reaches 52 ℃, Aldo
621 g of MS ester type lubricant was added. The temperature is 71
AC629A polyolefin wax 6 when reached ℃
9 g was added. When the temperature reaches 77 ℃, Paraloid K1
230 g of 75 (R) polymer lubricating aid and 2092 g of Paraloid KM355 (R) core-shell poly (butyl acrylate) // poly (methyl methacrylate) impact modifier were added.
This masterbatch was blended with a polypropylene copolymer in a reversing twin screw extruder with a polypropylene-acrylic graft copolymer and two antioxidants (Irgafos 168 and Cyanox 1790 0.2% each). The pelletized blend was injection molded. The table shows PVC has polypropylene hardness (Rockwell L), 264 psi DTUF
It is shown to increase L and elastic modulus.

[0089]

[Table 8]

Example 7 This example illustrates the use of two polar polymers to obtain blends with increased modulus at room temperature and elevated temperature.

55 parts by weight of polypropylene (Himont Pro-Fax 6523) in a co-rotating twin screw extruder, 45% by weight of a commercially available polycarbonate / polybutylene terephthalate blend (General Electric Xenoy 1101) and the polyolefin-acrylic graft of Example 2. A blend of 15 parts by weight of copolymer (B) was prepared. Next, the compounded pellets were injection molded into test pieces. A tensile tension of 279,000 psi at 23 ° C and a torsional modulus of 42,000 psi at 100 ° C were measured. For comparison, pure polypropylene (containing no polar polymer or graft polymer), which has been subjected to the same series of steps, has 2
Elastic moduli of 24,000 and 22,000 were obtained.

Example 8 This example illustrates the filler formulation. Co-rotating twin screw extruder 13.
A polypropylene / polycarbonate containing 8% filler was produced. This blend contains 1380 g of 20% calcium carbonate filled propylene copolymer, ABS 4
60 g, 160 g of the graft copolymer (B) of Example 2 and
It contained 4 g each of Cyanox 1790 and Irgafos 168. The pellets were injection molded and tested. This one has a non-notched impact strength of 12 ft-lb, a maximum tensile stress of 3820 psi,
DTUFL at moduli of 212,000 psi and 66 psi
It had a 98 ° C. and Rockwell hardness of 50 (L scale).

Example 9 This example demonstrates the effect of polycarbonate and compatibilizer on stiffness at room and elevated temperatures. Polycarbonate (General Electric Lexan 141), propylene impact copolymer (Rexene 9403, mfr 15) and polypropylene-acrylic graft copolymer (B) of Example 2 were blended in a co-rotating twin screw extruder. Testing was performed on injection molded samples.

[0094]

[Table 9]

Example 10 This example demonstrates the effect of polycarbonate and compatibilizer on stiffness at room and elevated temperatures. Co-rotating twin screw extruder polycarbonate (General Electric Lexan 141), polypropylene (Himont Pro Fax 6823, homopolymer mfr = 0.
4) and a polypropylene-acrylic graft copolymer ((B) of Example 2) were blended. This blend was injection molded and tested.

[0096]

[Table 10]

Example 11 This example demonstrates the effect of polyglutarimide on stiffness. Haake Rheoco
rd contains two polyglutarimides (about 76% by weight of N-methyldimethylglutarimide units, 19% by weight of units derived from methyl methacrylate, the balance being units derived from methacrylic acid / anhydride. Polymer P
GI-1 and N-methyldimethylglutarimide units about 86% by weight, units 1 derived from methyl methacrylate
PGI-, a polymer containing 4% by weight and essentially free of units derived from methacrylic acid / anhydride.
2), Propylene impact copolymer (Rexene 9403, mf
r = 1.5) and the blend of the polypropylene-acrylic graft copolymer (B) of Example 2 were blended. The lumps of this blend were pressed into plaques which were cut into samples.

[0098]

[Table 11]

Claims (15)

[Claims] 1. A) 100 parts of a polymer comprising at least 60% units derived from polypropylene; b) about 10 parts to about 175 phr of polar polymer (parts per 100 parts of propylene polymer); c) polyethylene. Polypropylene, polybutylene,
Poly (4-methylpentene), copolymers of the olefins with others, and 1 of the olefins with small amounts of 1-alkenes, vinyl esters, vinyl chlorides, (meth) acrylic esters and (meth) acrylic acid. At least one first segment selected from the group of polyolefins consisting of one or more copolymers; and the formula CH ₂ ═C
At least 80% of a monomer which is a methacrylic ester of (CH ₃ ) COOR (wherein R is alkyl, aryl, substituted alkyl, substituted aryl or cycloalkyl) and an acrylic or styrene monomer copolymerizable with the methacrylic ester. About 3 to about 35 parts of a compatibilizing polymer which is a segmented copolymer consisting of at least one second segment covalently linked to the first segment derived from less than about 20% of the body. D) optionally up to about 5 parts of an additive which is at least one of antioxidants, anti-ozone agents, UV stabilizers, antistatic agents, colorants, lubricants or processing aids; e) optionally Is a blend of about 5 to about 200 parts of an additive which is at least one of an impact modifier, a reinforcing filler, a non-reinforcing filler, a flame retardant or a plasticizer. 2. The polyolefin segment comprises about 50,
The blend of claim 1 having a weight average molecular weight of 000 to about 1,000,000. 3. The second segment is about 20,000-
The blend of claim 1 having a weight average molecular weight of about 200,000. 4. The blend of claim 1, wherein the polar polymer is polyglutarimide. 5. The blend according to claim 1, wherein the polar polymer is a styrenic polymer. 6. The blend of claim 1 wherein the polar polymer is an acrylonitrile-butadiene-styrene polymer. 7. The blend of claim 1 wherein the polar polymer is polyalkylene terephthalate. 8. The blend of claim 1, wherein the polar polymer is polycarbonate. 9. The blend of claim 1, wherein the polar polymer is a polyamide. 10. The blend of claim 1 wherein the blend is an extruded composition. 11. The blend of claim 1 wherein the blend is a thermoformed composition. 12. The blend of claim 1 wherein the blend is an injection molded composition. 13. The blend of claim 1, wherein the blend is profile extruded. 14. The blend according to claim 1, wherein the segment type copolymer is a graft copolymer. 15. The blend according to claim 1, wherein the segment type copolymer is a block copolymer.