CA2207807C - Thermoplastic polymer composition and method of molding parts with reduced shrinkage - Google Patents

Thermoplastic polymer composition and method of molding parts with reduced shrinkage Download PDF

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Publication number
CA2207807C
CA2207807C CA002207807A CA2207807A CA2207807C CA 2207807 C CA2207807 C CA 2207807C CA 002207807 A CA002207807 A CA 002207807A CA 2207807 A CA2207807 A CA 2207807A CA 2207807 C CA2207807 C CA 2207807C
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composition
shrinkage
plastomer
amount
set forth
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CA2207807A1 (en
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Terrence Huff
James John Mcalpin
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ExxonMobil Chemical Patents Inc
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ExxonMobil Chemical Patents Inc
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/14Copolymers of propene
    • C08L23/142Copolymers of propene at least partially crystalline copolymers of propene with other olefins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29LINDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00Other particular articles
    • B29L2031/30Vehicles, e.g. ships or aircraft, or body parts thereof
    • B29L2031/3044Bumpers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0807Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815Copolymers of ethene with aliphatic 1-olefins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00Polymer mixtures characterised by way of preparation
    • C08L2314/06Metallocene or single site catalysts

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A thermoplastic polymer composition incorporating at least about 50 wt.% polypropylene, at least about 20 wt.% of an elastomer such as EP rubber and at least about 4 wt.% plastomer. The plastomer is preferably a single site catalyzed ethylene based copolymer having a density less than about .915 g/cm3. By adjusting the amount of the plastomer in the composition, considerable control is secured over post-mold shrinkage of components produced through injection molding operations utilizing the composition. The composition can be prepared as a reactor blend or a melt blend. The composition is particularly useful in producing large components such as bumpers and exterior trim fascia for automobiles.

Description

THERMOPLASTIC POLYMER COMPOSITION AND METHOD OF MOLDING PARTS WITH REDUCED
SHRINKAGE
FIELD OF THE INVENTION
This invention relates generally to thermoplastic polymer compositions and to their production and use. More particularly, this invention relates to thermoplastic olefin polymer compositions incorporating narrow composition distribution olefin based plastomers and to the manner of producing and using such compositions.
to BACKGROUND OF TFdE INVENTION
Thermoplastic elastomers (TPEs) are an important class of polymers which are particularly useful in producing durable components through injection molding processes. A typical TPE structure is a matrix of a plastic component with discrete domains of an elastomeric component embedded therein. This structure yields a composite having a behavior similar to a cured elastomer but with the advantage that it undergoes plastic flow above the softening point of the plastic component.
This permits. TPEs to be used in components fabricated through thermoplastic injection molding. Such molding processes are generally impractical with conventional cured elastomers, because they do not undergo plastic flow at 2o elevated temperatures.
Thermoplastic olefins elastomer (TPOs) are a class of TPEs based predominantly or wholly on olefin polymers. A typical TPO is a melt blend or reactor blend of a polyolefin plastic, typically polypropylene, with an olefin copolymer elastomer (OCE), typically an ethylene-propylene rubber. The polyolefin plastic imparts to the TPO the temperature resistance and rigidity typical of that resin while the elastomer provides flexibility, resilience and toughness.
TPOs are particularly well suited for producing flexible structures such as body parts for automotive applications. The principal automotive applications include bumper covers, exterior fascia, air dams and other trim, dashboard skins, 3o and airbag covers. Various TPO formulations are available having physical WO 96/19533 PCT/US9511~239 properties highly desirable in such applications. The ability of TPOs to be injection molded makes them particularly attractive for the high volume production necessary in automotive applications.
One disadvantage of TPOs, and indeed of TPEs generally, is that in most injection molding processes they are subject to significant post molding shrinkage.
For most TPO formulations the linear shrinkage in a typical injection molding operation is in the range of 1.0-2.0%. This generally does not cause any degradation in the properties of the completed product, but does mean that in applications where dimensional tolerances are important the mold must be tailored 1o to the TPO formulation and the specific molding operation (e.g. the degree of cooling allowed prior to mold ejection) to yield a finished part of the precise dimension required. This shrinkage problem is particularly troublesome where the manufacturer has produced molds tailored to one TPO formulation and molding process and subsequently wishes to substitute a different TPO formulation or alter the process (e.g. increase the cooling rate). The substitution may result in a changed degree of shrinkage, yielding parts which are out of dimensional tolerance.
One solution to this problem is to employ additives in the TPO composition which assist in controlling shrinkage. Talc and other inorganic particulate materials are sometimes used for this purpose. Such shrinkage control additives carry with them disadvantages, though. They tend to reduce flexibility, decrease toughness, and degrade the surface finish of the completed part.
An alternative to shrinkage control agents is to alter the formulation of the TPO to increase the content of the elastomeric component relative to the plastic component. This entails several disadvantages: 1) it increases the cost of the TPO, since the elastomer is generally the most expensive component of the blend;
2) increasing the elastomer content degrades the melt flow behavior of the composition; and 3) as the elastomeric content is increased, it becomes increasingly ' difficult to disperse the elastomer within the plastic component.
It would .be desirable to develop formulations for TPOs and other 3o thermoplastic polyolefins to yield compositions which have reduced shrinkage but which do not introduce processing difficulties or materially degrade the physical properties of the finished part or increase its cost.
SUMMARY OF THE INVENTION
We have discovered that by incorporating plastomers into certain polyolefin compositions, blends axe obtained which have reduced post mold shrinkage in injection molding applications. This ability to control shrinkage through the introduction of plastomers appears to be most pronounced for polypropylene based TPO's with relatively high flexural modulii. The preferred plastomers for this application are metallocene catalyzed ethylene based copolymers with densities in the range of .87-.90 g/cm3.
An inorganic filler material can be added to provided additional shrinkage control and to counteract the decrease in flexural modulus typically resulting from the incorporation of the plastomer.
While the present invention appears to be most beneficial in shrinkage control of TPOs, it is also useful in controlling shrinkage of isotactic polypropylene homopolymers, random polypropylene copolymers, impact polypropylene copolymers and other thermoplastics used in injection molding and other applications in which shrinkage control is desirable.
Thus, according to a first aspect of the invention, there is provided a thermoplastic polymer composition, comprising:
polypropylene in an amount of at least 50 wt % of the polymer component of the composition;
elastomer in an amount of at least 20 wt % of the polymer component of the composition;
plastomer in an amount of at least 4 wt% of the polymer component of the composition, the plastomer having a melt index in the range of 0.5 to 50 g/10 min, a density in the range of 0.86-0.92 glcm3, and a molecular weight distribution (MWD) <
3.5; and optionally, a shrinkage control additive, preferably, in an amount less than 15 wt of the total composition.

According to a second aspect of the invention, there is provided a polymer composition, comprising:
polypropylene in an amount of at least 50 wt% of the polymer component of the composition;
elastomer in an amount of at least 20 wt% of the polymer component of the composition;
plastomer in an amount in the range of 2-15 wt% of the polymer component of the composition; and at least one shrinkage control additive in an amount sufficient to reduce the post mold shrinkage of the composition in an injection molding application by at least 10% relative to shrinkage in the absence of the shrinkage control additive.
In a preferred embodiment of the invention, the polypropylene is a propylene based copolymer, such as a random copolymer of propylene and ethylene, and the plastomer is a metallocene catalysed, ethylene based copolymer.
In a further preferred embodiment of the invention,the plastomer constitutes in the range of 4-15 wt.% of the polymer component of the composition.
In yet a further preferred embodiment of the invention,the plastomer constitutes in the range of 4-12 wt% of the polymer component, and wherein the plastomer is a copolymer of ethylene and at least one C4-C20 alpha-olefin.
In yet a further preferred embodiment of the invention,thecomposition incorporates at least 10% by weight of an inorganic filler.
In yet a further preferred embodiment of the invention,the plastomer is added in an amount sufficient to reduce the shrinkage of the composition in an injection molding application by at least 10% relative to shrinkage in the absence of the plastomer.
In yet a further preferred embodiment of the invention,the filler and the plastomer are collectively added in an amount sufficient to reduce shrinkage by at least 30%, preferably at least 40% relative to shrinkage in the absence of the filler and plastomer components.
In yet a further preferred embodiment of the invention,the flexural modulus is within 20% of the flex modulus in the absence of the filler and plastomer components.
-3a-In yet a further preferred embodiment of the invention, the polypropylene and elastomer are in the form selected from the group consisting of a thermoplastic olefin elastomer (TPO) and an impact copolymer (ICP).
In yet a further preferred embodiment of the invention,the polypropylene and rubber are produced in a continuous reactor TPO process.
According to a further aspect of the invention, there is provided a method for producing an injection molded part in a mold, the part comprising a thermoplastic polymer composition and the part having a desired degree of shrinkage relative to the mold, the method comprising:
a) determining said desired degree of shrinkage for a selected set of molding conditions;
b) blending the following components to form the polymer composition:
polypropylene in an amount of at least 50 wt % of the polymer component of the composition;
elastomer in an amount of at least 20 wt% of the polymer component of the composition;
plastomer in an amount of at least 4 wt% of the polymer component of the composition, the plastomer having a melt index in the range of 0.5 to 50 g/10 min, a density in the range of 0.86-0.92 g/cm3, and a molecular weight distribution (MWD) <
3.5; and c) molding the part using the selected set of molding conditions.
In a preferred embodiment of the invention, the blending step further includes adding at least 10 wt% of an inorganic filler material.
According to yet a further aspect of the invention, there is provided a method for producing an injection molded part for a vehicle in a mold, the part comprising a thermoplastic polymer composition, and the part having one dimension of at least 1 meter and a desired degree of shrinkage relative to said mold, the method comprising the steps of:
a) determining said desired degree of shrinkage for a selected set of molding conditions;
-3b-b) preparing a thermoplastic olefin composition by blending polypropylene in an amount of at least 50 wt % of the polymer component of the composition with elastomer in an amount of at least 20 wt % of the polymer component of the composition;
c) adding to the thermoplastic olefin composition an amount of a metallocene catalyzed plastomer sufficient to provide a reduction of the post-molding shrinkage of the composition of at least 10 % relative to shrinkage in the absence of the plastomer to yield a thermoplastic polymer composition having the desired degree of shrinkage;
and d) molding the part using the selected set of molding conditions.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Introduction Our invention concerns improvements to thermoplastic olefin elastomer compositions ("TPOs "), impact copolymer compositions ( "ICPs") and certain other thermoplastics. These improved TPOs and ICPs are particularly useful for injection molding applications in which it is desirable to achieve a specified low degree of post mold shrinkage. Following is a detailed description of certain preferred compositions within the scope of our invention, preferred methods for -3c-producing these compositions, and preferred applications of these .composit.ions.
Those skilled in the art will appreciate that numerous modifications to these preferred embodiments can be made without departing from the scope of the invention. For example, though the properties of the compositions are exemplified in injection molding applications, the compositions have other uses. Also, while the invention will be exemplified principally in connection with TPOs, it will be understood that the invention is also applicable to ICPs, polypropylene RCPs and other thermoplastics used in applications in which shrinkage is an issue. To the extent that our description is specific, this is done solely for the purpose of to illustrating certain preferred embodiments of our invention and should not be 'taken as restricting our invention to these embodiments.
We have discovered that by incorporating relatively small amounts of plastomers (as defined below) into TPOs and certain other thermoplastic compositions, considerably improved compositions can be obtained. A principal advantage of these compositions is that a modest inclusion of plastomer yields a surprisingly great reduction in post mold shrinkage of parts produced through injection molding processes using the compositions. We have found that. it is straightforward to relate the degree of shrinkage to the amount of plastomer utilized in the composition, for a given base resin and given molding operation.
2o This allows a resin supplier to provide compositions tailored to have whatever reasonable degree of post-mold shrinkage is desired by the customer.
Metallocene catalyzed polyethylene copolymers with densities in the range of .87-.90 g/cm3 are the preferred plastomers for use in this invention. Shrinkage control is not the sole benefit of the invention. The incorporation of plastomer also enhances low temperature impact strength and provides other advantages.
Another key aspect of our invention is that plastomers can be a sed in conjunction with conventional shrinkage control agents such as talc. The resulting compositions derive much of the cost savings provided by the inexpensive filler while avoiding to a significant degree the degradation in physical properties which 3o typically occurs when such fillers are used in greater amounts.
Composition and Production of the Base TPOs For the purpose of this description and the appended claims, the term "thermoplastic olefin polymer" ("TPO") shall mean those blends of polypropylene and rubber which are substantially thermoplastic and have a flexural modulus in the range of 40,000-180,000 psi (276-1240 MPa). Most typically, TPOs have a polypropylene content in the range of 50-80 wt% and a rubber content in the range of 15-50 wt%. The polypropylene may be homopolypropylene, propylene based copolymers or combinations of the two. The term "polypropylene", as used in this description and the appended claims, is defined to mean any propylene based io polymer having a propylene content of at least 80 wt%. In most applications it will be desirable that the polypropylene phase be continuous or nearly continuous.
The rubber phase exists in discrete domains dispersed throughout the polypropylene phase. Most commonly, the rubber will be an ethylene-propylene rubber or an ethylene-propylene terpolymer rubber, however, other rubber compositions may be used. The term "elastomer", as used in this description and the appended claims shall mean any essentially non-crystalline polymeric component having a low glass transition temperature (typically <_ -35°C). The base TPO may also include additional olefin polymers, fillers, pigments, stabilizers and property modifiers. Further details regarding the composition and properties of 2o TPOs are set forth in U.S. patents 3,806,588, 4,143,099, 5,023,300 and 5,210,139.
The manner in which the base TPOs are produced is not critical to the present invention. They can be produced by conventional melt blending of the individual components, by "reactor blending", by combinations of these two processes, or other means which achieves a dispersion of discrete elastomer regions within a substantially continuous polypropylene matrix.
In the preferred method of producing base TPOs, a random propylene ethylene copolymer is produced in an initial bulk liquid polymerization step 3o conducted in a reactor. In some processes, multiple reactors may be employed for this step. The copolymer is preferably about 3 wt.% ethylene and has a very high molecular weight, preferably above 500,000 M~ (viscosity average molecular weight). The product of the bulk liquid polymerization step is then fed to a gas phase reactor in which a 60 wt.% EP ethylene elastomer is produced. The process is controlled such that the EP elastomer addition to the propylene-ethylene copolymer is in the range of 18-28 wt.%, preferably about 20-26 wt.%, based on the combined weight of the elastomer and the copolymers. To this granular reactor product, a stabilizer and a peroxide are added to allow visbreaking in a following extrusion step conducted in an extruder. The amount of peroxide and the extruder to operating conditions are controlled such that the extruded reactor TPO has the desired melt flow rate. By maintaining a very high molecular weight in producing the polymerization steps and then visbreaking the copolymer in the extrusion si:epto yield a lower molecular weight product, a reactor TPO of the desired melt flow rate can be efficiently produced while avoiding potential fouling in the liquid 15 polymerization step. The desired quantity of plastomer (as described more fully below) may be added at the feed point of the extruder. Further details of producing the reactor TPO are taught in U.S. patents 5,023,300 and 5,210,139, referenced above.
20 The Plastomers and their Incorporation into the TPO
In a preferred embodiment, the TPO of the present invention includes i.n the range of about 2-40 wt% plastomer, more preferably 3-20 wt%, yet more preferably 4-1 S wt% and most preferably 5-12 wt%. For the purposes of this application, the term "plastomer" shall mean ethylene based copolymers having a 25 density in the range of about .86-.915 gm/cm3. In many embodiments it will be desirable to use the lowest density plastomer consistent with maintaining good handling of the plastomer resin. In warm climates, it will often be desirable to use densities above about .890, to avoid the need for chilled resin storage, due to cold flow of lower density resins having the desired melt index. The preferred.
melt 3o index range of the plastomer is in the range of about .5-40 g/10 min, with 1..0-10 g/10 min being most preferred. In some applications it will be desirable to select a plastomer having a melt index near that of the base TPO blend.
The preferred plastomers for use in the present invention are those produced utilizing metallocene catalysts. Most preferred are those ethylene based copolymer plastomers sold under the trademark Exacft'M, available from Exxon Chemical Company of Houston, Texas. These plastomer have a plastic-like molecular weight for better dispersion in polypropylene. They are also free of exterior dusting agents and interior processing aids which could adversely affect the properties of the TPO. The invention can also be practiced using EngageT's 1o polymers, a line of metallocene catalyzed plastomers available from Dow Chemical Co. of Midland, IVl;ichigan. Metallocene catalyzed plastomers are characterized by narrow molecular weight distribution (typically in the range of 1.8 - 3.5), low ash content, and narrow composition distribution.
The composition distribution is a measure of the variance in comonomer 1s content among the polymer molecules. One measure of the composition distribution is the composition distribution breadth index, or "CDBr', which is a measure of what fraction of the molecules have a comonomer content within ~
25% of the mean comonomer content. The CDBI can be measured utilizing temperature rising elution fractionation techniques.
2o The preferred plastomers for use in the present invention have a CDBI of at least 45%, preferably at least 50% more preferably at least 60% and most preferably above 70%. They have a MWD of below 4.0, preferably in the range of 1.7 - 3.5, more preferably in the range of 1.8-3.0 and most preferably in the range of 1.9 - 2.8. They have a density in the range of .865 - .92 g/cm3; preferably in the 25 range of .87-.91 g/cm3, more preferably in the range of .88 - .905 g/cm3, and most preferably in the range of .885-.900 g/cm3. The preferred comonomers are non-cyclic mono-olefins such as butene-1, pentene-1, hexene-1, octene-l and 4 methyl-pentene-1. However, cyclic mono-olefins and both linear and cyclic dienes can WO 96/1933 PCTlUS95/16~239 also be used. It will be desirable in some applications to use ethylene, alpha-olefin, dime terpolymers. This is advantageous in that it provides the plastomer with , residual unsaturation to allow a functionalization reaction or cross-linking in the rubber phase of the finished product.
The manner in which the plastomer is incorporated into the TPO is not critical, provided it is well dispersed throughout at least the rubber component of the TPO. For reactor TPOs, the plastomer can be incorporated by addition of plastomer pellets immediately upstream of the pelletizing extruder.
Alternatively, it can be added by the TPO producer or by a compounder in a compounding step to after production of the TPO, or by the converter in a blending process prior to fabricating the end product. For compounded TPOs, the plastomer can be added at the time of melt blending. Alternatively, the plastomer can be pre-blended with the rubber component, with the rubber-plastomer blend later being compounded with the polypropylene in producing compounded TPOs.
Properties and Applications of the Present TPO Compositions The addition of plastomer to TPO compositions imparts numerous property advantages. As discussed in greater detail below, one of the key advantages is reduced post mold shrinkage. Other advantages include an increase 2o in the low temperature impact strength, improved surface gloss and appearance, improved resiliency and some reduction in opacity. The plastomer also works a significant decrease in the flexural modulus of the TPO, which will be advantageous in many applications. In some applications, the addition of plastomer will also enhance the processability of the finished composition.
Naturally, certain debits are also associated with the inclusion of a plastomeric component. Both surface hardness (i.e. Shore D) and tensile strength at yield will decrease as plastomer content increases. Such debits can often be accommodated by selecting a base TPO with a higher surface hardness and tensile strenth at yield than the desired ultimate values.
_g_ Table I provides data illustrating the shrinkage reduction imparted by the inclusion of plastomer into two commercially available reactor TPOs. The blending was accomplished by adding the plastomer in an extrusion step to the reactor TPO production process product. In a commercial operation, this plastomer addition would preferably be made to the post reactor extruder in the reactor TPO production process. Note that a modest addition of plastomer yielded a surprisingly great degree of shrinkage control for the stiff TPO (PD 8154).
The effect was not as pronounced in the soft TPO (PD8191). Tables 2-4 identify the resins employed in the tests. Table 5 recites the test methods employed.
1o By adjusting the amount of plastomer in the blend, any degree of shrinkage control, in many instances down to at least about 0.35%, can be secured. This is particularly useful in developing substitute TPOs for an existing application.
As discussed above, molds , used in injection molding parts are adapted to a specific TPO grade and process so that the finished part in exactly the desired size.
This has had the effect of locking an injection molder into a specific TPO grade due to the difficulty and expense in identifying another TPO grade with the same shrinkage characteristics for that process. The present invention allows the post mold shrinkage to be readily adjusted without, in most instances, any major adverse impact on other properties.
TPOs Incorporating both Plastomers and Other Shrinkage Control Additives In some applications it will be particularly advantageous to utilize both plastomer and an inorganic filler or other shrinkage control additive in a TPO
composition. It is well known to employ such inorganic additives as talc, calcium carbonate, mica, certain clays and glass fibers for the purpose of achieving shrinkage control. Many other compounds known to those skilled in the art can be used for this purpose. The key properties of such shrinkage control agents is that they are inexpensive compared to the polymeric components of the TPO, they are substantially inert in the application, and they control shrinkage. The disadvantage of using such materials is that they generally have a net adverse impact on the physical properties of the TPO. For example, they typically degrade surface smoothness of molded parts, they raise the brittle temperature, they increase the modulus of elasticity (sometimes this is not a disadvantage), they degrade the ability to injection mold the TPO and they generally increase the density of the TPO material.
Many of the disadvantages of these fillers can be overcome by using them in conjunction with plastomers. The plastomer tends to improve most of the properties degraded by the filler. Where the filler degrades surface appearance, the plastomer improves it. Where the filler raises the brittle temperature, the plastomer io depresses it. Where the filler increases the modulus of elasticity, the plastomer decreases it. Likewise, the filler can improve certain potential disadvantages introduced by the plastomer. For example, where the plastomer decreses surface hardness, the filler increases it. Thus, by carefi>i selection of the relative amounts of plastomer and filler used in a TPO composition, it is possible to obtain a TPO
that is less expensive than the base TPO, has greatly reduced post-mold shrinkage than the base TPO, yet has substantially the same brittle temperature, modulus of elasticity and surface hardness as the base TPO. Those skilled in the art will appreciate that by varying the relative fractions of the plastomer and filler in the TPO a wide range of property mixes can be achieved.
2o Table 6 illustrates the shrinkage reduction available by blending both talc and various plastomers with Escorene PD 7565, an ICP available from Exxon Chemical Company of Houston, Texas. This is also illustrated in Composition G
in Table 1.
Those skilled in the art will appreciate that the compositions of the present invention have formulations, production methods, applications and advantages beyond those expressly recited herein. For example, as previously recited, though the present invention has been exemplified principally in connection with TPO
compositions, it is also applicable to ICPs, polypropylene RCPs and other thermoplastic olefin resins in which it is desirable to control shrinkage. The 3o coverage of this patent is limited only as set forth in the appended claims.
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Tabk 2 Polypropylene Copolymer Grade Melt Fiow Ethvlene Content~wt%Su lier hate Escorene* PD 11 15 Exxon Chemical Escorene* PD 1 17.5 Exxon Chemical Escorene* PD 45 8.2 EXXOn Chemical Tabk 3 Metallocene Plastomera Grade Melt IndezDenaitv Comonomer Sn iier EXAC1'~ 3055 3.5 0.9 Buttne Exxon Chemical EXACTT" 4033 0.8 0.88 Butene Exxon Chemical EXACT"' 4041 3 0.878 Hutene Exxon Chemical ENGAGET~ 8100 1 0.87 Octene Dow Chemical ENGAGE'~'~' 0.5 0.87 Octene Dow Chemical ENGAGE'm 8200 5 0.87 Octene Dow Chemical Table 4 Ethylene Propylene Rnbber ..e~,. .. __...
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Claims (19)

CLAIMS:
1. A thermoplastic polymer composition, comprising:
polypropylene in an amount of at least 50 wt% of the polymer component of said composition;
elastomer in an amount of at least 20 wt% of the polymer component of said composition;
plastomer in an amount of at least 4 wt% of the polymer component of said composition, said plastomer having a melt index in the range of 0.5 to 50 g/10 min, a density in the range of 0.86-0.92 g/cm3, and a molecular weight distribution (MWD) <
3.5; and optionally, a shrinkage control additive.
2. The composition as set forth in claim 1 wherein said shrinkage control additive is present in an amount less than 15 wt% of the total composition.
3. A polymer composition, comprising:
polypropylene in an amount of at least 50 wt% of the polymer component of said composition;
elastomer in an amount of at least 20 wt% of the polymer component of said composition;
plastomer in an amount in the range of 2-15 wt% of the polymer component of said composition; and at least one shrinkage control additive in an amount sufficient to reduce the post mold shrinkage of said composition in an injection molding application by at least 10% relative to shrinkage in the absence of said shrinkage control additive.
4. The composition as set forth in any one of claims 1-3 wherein said polypropylene is a propylene based copolymer and said plastomer is a metallocene catalysed, ethylene based copolymer.
5. The composition as set forth in claim 4 wherein said polypropylene is a random copolymer of propylene and ethylene.
6. The composition as set forth in any one of claims 1-5 wherein said plastomer constitutes in the range of 4-15 wt. % of the polymer component of said composition.
7. The composition as set forth in any one of claims 1-6 wherein said plastomer constitutes in the range of 4-12 wt% of said polymer component, and wherein said plastomer is a copolymer of ethylene and at least one C4-C20 alpha-olefin.
8. The composition as set forth in any one of claims 1-7 wherein said composition incorporates at least 10% by weight of an inorganic filler.
9. The polymer composition as set forth in any one of claims 1-8 wherein said plastomer is added in an amount sufficient to reduce the shrinkage of said composition in an injection molding application by at least 10% relative to shrinkage in the absence of said plastomer.
10. The polymer composition as set forth in any one of claims 1-7 and 9 wherein said shrinkage control additive and said plastomer are collectively added in an amount sufficient to reduce shrinkage by at least 30% , relative to shrinkage in the absence of said shrinkage control additive and plastomer components.
11. The polymer composition as set forth in claim 8 wherein said filler and said plastomer are collectively added in an amount sufficient to reduce shrinkage by at least 30%, relative to shrinkage in the absence of said filler and plastomer components.
12. The polymer composition as set forth in claim 10 wherein said shrinkage control additive and said plastomer are collectively added in an amount sufficient to reduce shrinkage by at least 40% relative to shrinkage in the absence of said shrinkage control additive and plastomer components.
13. The polymer composition as set forth in claim 11 wherein said filler and said plastomer are collectively added in an amount sufficient to reduce shrinkage by at least 40% relative to shrinkage in the absence of said filler and plastomer components.
14. The polymer composition as set forth in either claim 8 or claim 13 having a flexural modules within 20% of the flexural modules in the absence of said filler and plastomer components.
15. The polymer composition as set forth in any one of claims 1-14 wherein said polypropylene and elastomer are in the form of a thermoplastic olefin elastomer (TPO) or an impact copolymer (ICP).
16. The composition as set forth in claim 1 wherein said polypropylene and elastomer are produced in a continuous reactor TPO process.
17. A method of producing an injection molded part in a mold, said part comprising a thermoplastic polymer composition and said part having a desired degree of shrinkage relative to said mold, said method comprising:
a) determining said desired degree of shrinkage for a selected set of molding conditions;
b) blending the following components to form said polymer composition:
polypropylene in an amount of at least 50 wt% of the polymer component of said composition;
elastomer in an amount of at least 20 wt% of the polymer component of said composition;
plastomer in an amount of at least 4 wt% of the polymer component of said composition, said plastomer having a melt index in the range of 0.5 to 50 g/10 min, a density in the range of 0.86-0.92 g/cm3, and a molecular weight distribution (MWD)< 3.5;
and c) molding said part using said selected set of molding conditions.
18. The method as set forth in claim 17 wherein said blending step further includes adding at least 10 wt% of an inorganic filler material.
19. A method for producing an injection molded part for a vehicle in a mold, said part comprising a thermoplastic polymer composition, and said part having one dimension of at least 1 meter and a desired degree of shrinkage relative to said mold, said method comprising the steps of:
a) determining said desired degree of shrinkage for a selected set of molding conditions;
b) preparing a thermoplastic olefin composition by blending polypropylene in an amount of at least 50 wt% of the polymer component of said composition with elastomer in an amount of at least 20 wt% of the polymer component of said composition;
c) adding to said thermoplastic olefin composition an amount of a metallocene catalyzed plastomer sufficient to provide a reduction of the post-molding shrinkage of said composition of at least 10% relative to shrinkage in the absence of said plastomer to yield a thermoplastic polymer composition having the desired degree of shrinkage; and d) molding said part using said selected set of molding conditions.
CA002207807A 1994-12-16 1995-12-14 Thermoplastic polymer composition and method of molding parts with reduced shrinkage Expired - Fee Related CA2207807C (en)

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US08/357,635 US5747592A (en) 1994-12-16 1994-12-16 Thermoplastic polymer compositions and their production and use
US08/357,635 1994-12-16
PCT/US1995/016239 WO1996019533A1 (en) 1994-12-16 1995-12-14 Thermoplastic polymer composition and method of molding parts with reduced shrinkage

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