TW593499B - Elastomeric composition and its process for preparation and use - Google Patents

Abstract

An elastomeric composition that provides excellent abrasion resistance and is useful for producing fabricated articles includes a plasticizer and a crystalline polyolefin phase that is either continuous or co-continuous with an ethylene/alpha-olefin polymer phase. Certain compositions also contain a material that enhances Wet COF of the composition, and in some instances, processibility of the compositions. Other compositions obtain the same enhancement by choice of process conditions. The resulting articles also have an enhanced Wet COF.

Description

Employees' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, Cooperative Printing Poly A7 -------- V. Description of the Invention (1) Field of the Invention The present invention relates generally to elastomeric compositions, which comprise an elastomeric ethylene / α-ene polymer (ΕΑΟ) polymerization. And a crystalline polyolefin (Cp), preparation of the composition, use of the composition in methods such as shape extrusion and injection molding, and manufacture of articles such as soles other than shoes formed by such methods. The present invention is particularly relevant to these compositions, in which the CPO forms a phase that is at least co-continuous with the phase formed by the EAo polymer, the method of preparing the composition, the use of the composition, and the method of making the formed article. <The present invention also relates to compositions modified with a coefficient of wear (COF) reinforcement (COFE) material. When added to a composition, the COFE material provides a wet stone-brick COF (hereinafter, "wet COF") that is higher than a composition obtained without the COFE material, which is in accordance with ASTM D-1894 Measured. The present invention also relates to specific COF-containing compositions, which have improved processability compared to compositions without COFE materials. The present invention also relates to a variation of a manufacturing method that does not include CO. FE materials are used to make elastomeric compositions with improved wet coF. Background of the Invention W · K. Fischer has proposed a number of issues regarding an ea〇 polymer and a polyolefin blend. For example, usp 3,758 643 And usp 3 806,588-Contains an EA〇 polymer and a polyolefin admixture sufficient for maturation 7F. USP 3,835,201 reveals at least two different ... unsaturation of monoolefins with small amounts of copolymerizable non-conjugated diene彳 Like rubber copolymers and resin high-molecular-weight f (MW) poly-α-monoolefin plastics (such as pp) are "un" blended. The rubber copolymer has a high minimum shear viscosity or a melt viscosity lower than the minimum shear rate. Because these copolymers cannot form a band on the cold mill, it is "quoted in this paper as the standard ^ 7CNS) (Please read the precautions on the back before filling in this I) Printed by the Consumer Standards Cooperative of the Central Bureau of Standards 593499 5. Description of the Invention (2 It is considered to be unprocessable. USP 3,682,106 relates to a thermoplastic trade-state ripening blend of EA0 copolymer and polyfluorene. Partial ripening and dynamic ripening ^ make it impossible Increased soluble gel content. Insoluble gel content (gelatin) test using cyclohexane at 23 ° C. An acceptable alternative is boiling xylene, a customary solvent that produces gels Thallium is 30-50% lower than those produced using cyclohexane. Fischer proposed various examples when the partially vulcanized or dynamically cured composition was extruded into an eight-inch long rod, where the level of gel particles was so low that it became impossible. Accepted Thickness.

Mike Wilson at "Slip Resistance perf〇rmance 〇f s〇1 —

Materials' S_ATRA Bulletin. May 1996, pages 77-79, published by SATRA Footwear Technology Centre. On page 78, it is recommended that the minimum wear coefficient (C0jp) of outer soles and heels on dry and wet stone bricks is 〇 ·. 3. On page 79, he also suggested that sports shoes and industrial shoes have higher requirements for non-slip resistance, so C0F is at least 0.4, and sometimes at least 0.6. Summary of the Invention. One aspect of the present invention is an elastomer composition comprising: a. CP20 from 20 to 50 parts by weight (pbw) (based on the total weight of a and b), which is selected from the group consisting of polypropylene (PP) homopolymer and propylene / ethoxylate (p / E) copolymers; b. Elastic EA polymers from 80 to 50 pbw (based on the total weight of a and b), the polymer optionally has Polymeric dienes;-'/ / / c. From 1 to 200 pbw (for every 100 pbw EAO /)' plasticizer, the plasticizer is selected from the group consisting of fe oils and acid-based fe-based g Purpose category; and optional Ή d. A material from 0 to 40 pbw (for every 100 pbw a and 6¾ words), ____ -5- This paper size applies the Chinese National Standard (CNS) A4 specification (210x297 mm) ) -------- «Batch --- (Please read the precautions on the back before filling out this page) Order 593499 B7 — V. Description of the invention (3 The wet COF provided by it is higher than that containing only a, The wet friction coefficient of the composition of b and c. 'The elastomer composition preferably has CPO and EA0 polymers as two different phases. It is better that the CPO phase and the EAO phase are at least co-continuous. The abrasion resistance of the composition Sex (ASTMD16jO- 83, NBS Abrader) must be greater than (&gt;) the abrasion resistance of a single-phase composition made from the same component but having only EAO polymers. Unless otherwise stated, all ranges of g in this application include two The second aspect of the present invention is a method for preparing the composition of the first aspect, the method comprising blending a composition in two phases sufficient to form a crystalline polyolefin-based = EAO polymer phase in at least a co-continuous phase. Under the conditions of temperature, shear and pressure of the composition, the composition comprises: a. 2〇_5〇pbw (: = and: total weight as the basis) is selected from the group consisting of polypropylene homopolymer and propylene / ethylene copolymer CPO; b. 80-50 0 pbw (total weight of a and b is mwrk Lima Lane early) &lt; Elastic £ A〇 polymer, this EAO polymer selective polymerization has a kind-say from one, cloth early body ; C. 1-200 pbw (elastic EA0 polymer per 100 pbw) of Si 噌 South 噌 Si, lick plasticizers are less selected from the group consisting of e-liquid and citric acid; d η / 1/1 λ, α. Mesh 0, pbw (per 100 pbw a and b) provides a wet COF higher than the central standard of the Ministry of Economic Affairs of only g, g, a, b, and c compositions The employee friction cooperative prints the wet friction coefficient. This second aspect has one of two important related aspects. Relative to a similar composition that does not include the COFE material, the amount of CDFE material included in the wet type C0 to improve the two phases formed Take thing. Formula COF. On the other hand, a and b are placed under the conditions of temperature shear and pressure of the material, and then the ‘reference, fusion and combination’ is the combination of the fusion and combination.

^ 93499 A7 B7 printed by the Consumer Cooperatives of the Central Bureau of Standards of the Five Ministry of Economic Affairs' Invention Description (4 and c are placed under the conditions of temperature shear and pressure to form a two-phase blend composition, the wet type of the two-phase composition. 0? &Gt; Wet type of a two-phase composition formed by a single interactive reaction under conditions of temperature shear and pressure. The conditions for forming the first melt blending composition and the The conditions for the first melt blending composition to form a two-phase composition are preferably the same. The third aspect of the present invention is an article having at least one component made from the composition of the first aspect of the present invention. The composition includes at least one filler It is better. The next paragraph is a brief description of the drawing, including the manufacture of objects suitable for partial compaction. Brief description of the drawing Figure 1 is a comparative example (c0 Εχ) Β I transmission electron micrograph (tem), magnification 7 500 ×, which shows PP-light color material-series discontinuous phase, and ethylene / propylene 'difluorene monomer (EPDM) -dark material-series continuous phase. The ruler at the bottom of the micrograph shows a Micrometer. Figure 2 shows the TEM of the composition of Example (EX) 4 with a magnification of 7, 500χ, its light and dark materials are PP and EPDM, respectively, which are at least co-continuous phases. The preferred specific examples detail the use of conventional polymer manufacturing methods such as those described above to make the composition of the present invention into various shaped articles. The The composition is particularly suitable for the production of injection-moulded oak moons, and pieces such as outer soles or component bottoms and extruded plates and shaped articles such as cymbals and airtight devices. Some (but not all) applicable shaped articles G includes pi car body parts, bumper gauge boards, car body side moldings, exterior trim, interior trim, air damping, air / pipes, wheel covers and dashboard skins, and non-automotive applications such as polymers胄, polymer boards, garbage cans, storage containers, strips or belts of weeders, weeders, lawnmowers and other gardening equipment (Please read the precautions on the back before filling this page}

593499 A7 B7 V. Description of the invention (5 Please read the precautions of the back and then fill in _ This book is a page-mounted part, a rest car part, a golf cart part, a utility vehicle part and a water boat part. The composition also Can be used in roof applications, such as roofing films. The composition can additionally be used to make shoe components, such as the shaft or sole of a boot, especially industrial work boots. If the composition contains a questionable formula CQF I CGFE material, or a treatment piece sufficient to enhance wet COF, or both, the composition is particularly suitable for applications such as specific piping, industrial whip soles, sporting object grips, and automotive thermoplastics Polymer, polymer (TPo) and thermoplastic polyalkylene hydrocarbon (butadiene pv) applications, such as doorknobs, universal discs and armrests. The latter composition is also quite suitable for manufacturing to coat objects. Those skilled in the art are familiar This list can be added without experimentation. The elastomer composition of the present invention is substantially free of cross-linking, but includes a p0 elastic EA0 polymer, a plasticizer, and a selective one ^ In the case of my father's affiliation or maturation, the elastomer composition is a real, insoluble, and insoluble gel as proposed by w. K. Flscher. The I: Contains! In the range from 50 to 20 Pbw Here, these two percentages are printed as 100 I WCP 0 Ma Jia with ΕΑ〇, ^ 6〇-Β〇pbw ΕΛ0 ^, the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs. The total content of this content is I 100pbw. p W ΕΑΟ polymer also contains plasticizers from 1 to 200. P mesh 5 {M) 0 pbw co = = hair f compound (㈣ is :, ethyl 晞 物 ,,) including (EP) co ^ Butadiene copolymers. Exemplary polymers include ethene / propane κ ethylene / butylene (EB) copolymers, ethene / octene (E0) co-/-olefins / diene monomers (EA). DM) A total of 'abandoned. Yang, such as the second party, / acrylic one quasi-one-home-country-country f, with a suitable ruler, a piece of paper I

SN one centimeter A7 invention description (7 or by ASTM D_123 8 (190 ° C, 10 kg weight) Canrong index (1⑷ to the ratio (11 () / 12) can also be measured. 、 .12 '' copolymer "Means a polymer in which at least two kinds of monomers are polymerized. It includes, but is not limited to, copolymers, trimers, and tetramers. It particularly incorporates, and polymerizes B '; cloth and A polymer made from at least one comonomer, which is usually an α-olefin of 3-20 carbon atoms (c3-C20), preferably 3-10 fluorene atoms (cc species. Applicable α -Examples of olefins include propane, 1-butene, 1-hexene 10) methyl-1-pinene, 1-heptene, 1-octane and styrene. Preferred copolymers include EP, EB, ethylene / Hexene · 1 (ΕΗ) and EO polymers. Exemplary terpolymers include ethylene / propylene / octene terpolymers and terpolymers of ethylene-ene, CrCua, alkane = non-conjugated diene monomers. The non-conjugated difluorene monomer may have one polymerized double bond, such as one of 5-ethylidene-2-orthobornadiene (ENB) ^ two: a double bond such as one of orthobornadiene (NBD) The diene monosystem is selected from the group consisting of NBD, dicyclopentadiene, ι, 4-hexane Diphenyl, pentylene, enb and = mixtures are preferred. Tetramers are made from more than one CrCMt olefin or more than one non-conjugated difluorene monomer. Those skilled in the art can easily select any desired copolymerization Applicable monomer combination for material use. “Elasticity,” as used in this article printed by the Employees' Cooperatives of the Central Standards Bureau of the Ministry of Economics, means an EA0 polymer with a density preferably less than (&lt;) 0.910 g / cm3 (g per (Cubic cm), preferably &lt; 0.900 g / cm3, &lt; 0.895 g / cm3 is better, &lt; 0.888 g / cm3 is more preferred, 0.850-0.880 g / cm3 is good, 85〇_〇87〇g / cm3 is more preferable, the crystallinity percentage &lt; 33%, ^ M% is more preferable, &lt; M% is better. The density is greater than (&gt;) 0.850g / cm3. Crystallization Degree percentage is measured by differential scanning calorimeter (DSC). ， '· ， ·. -10- This paper size is applicable to China National Standard (CNS) A4 specification (210X29 * 7 mm 593499 A7 B7 V. Description of the invention (8) SLEPs are characterized by a narrow MWD and a narrow short-chain branching distribution (SCbd), which can be as described in the US patent (U SP) described in Nos. 5,272,236 and 5,278,272. Preparation 'The relevant sections are presented for reference. Due to MWD and LCB-related matters, S C B D, S L E P s shows excellent physical properties.

USP 5,272,23 6 (5th row, 7th row, 6th column, 28th row) describes the manufacture of SLEP, which uses at least one reactor (multiple reactors are also possible), sufficient to manufacture SLEP with the required properties The polymerization temperature and pressure are controlled by continuous polymerization. The polymerization is carried out by a dissolution polymerization method, and the temperature is from 20 ° C. 〇-250 C ′ It is better to use mandatory geometric catalyst (CGC) technology. The applicable CGC is disclosed in USP 5,2? 2,236, column 6, line 29 to line I3, line 50. Che Fujia's SLEP has several obvious characteristics, one of which is the content of B-wife is 20-90 weight percent (wt%), 30-80 wt% is better, and the rest includes one or more comonomers. The ethylene and comonomer content is based on SLEP weight and the total monomer content reaches 100 Wt%. Other obvious SLEP characteristics include the melting index (j2) (ASTm D-1238 'condition 190 C, 2.16 kg weight (Formerly condition E)) and MFR or 11/10/12. 12 of the copolymer is preferably 0.01-30 g / 10 minutes, 0.01-10-printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) g / 10 minutes Better. The SLEP's I10 / I2 (ASTM D1238) is also &gt; 5.63, preferably 6.5-15, and more preferably 7-10. In terms of SLEP, the IlQ / l2 ratio is used as an indicator of the degree of LCB, so a larger ratio of 110 / 〖2 indicates that it is in the polymer. The LCB degree is higher. / SLEPs that meet the aforementioned standards include, for example, The Dow Chemical

Company and DuPont Dow Elastomers LLC's ENGAGE® Poly-11-This paper size applies to Chinese National Standard (CNS) A4 (2lOX 297). Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 593499 5. Description of Invention (μ) The amount of peak injection molding pressure of a polymer composition is lower than the group without the polymer ::: material holding force. :: The second related aspect of the second aspect replaces the composition containing the COFE material I with a similar comparison result. ^ Sub-polymers with dual-mode or multi-mode MWD can also be used as COF materials as long as they have a low-MW portion that meets the aforementioned head characteristics I. Because it is generally believed that the low MW part reinforces the coF, those skilled in the art will understand that a larger amount of dual-mode or multimode EAo polymer must be used to achieve an effect equivalent to that of a low-polymer. The &quot; adhesive &quot;, as used herein, is a general term for any hydrocarbon substrate composition, which is used to impart a lip tack to a hot melt adhesive composition. Some adhesives also have polar components. Exemplary adhesives include aliphatic Cs resins, polyterpene resins, hydrogenated resins, mixed aliphatic and aromatic resins, hydrogenated mixed aliphatic and aromatic resins, turpentyl esters, and hydrogenated turpentyl esters. The viscosity of the adhesive at 350 degrees Fahrenheit (τ) (1 77 C) (measured by Brookfield viscometer) is usually not more than 300 centipoise (0.3 basca-second), glass transition temperature (tin g) &gt; 25 ° C. The Tg is in the range of 25 ° C -120 ° C, preferably 40 ° C -100 eC. Commercially available adhesives include aliphatic resins (AdTac®, Piccotac® and

Piccopale® (Hercules Inc.)), Moon purpose / aromatic resins (Hercotac® and Piccolytely (Hercules, Inc.)), pure monomer resins (Endex®, Piccolastic®, Piccotex® and Kristalex® (Hercules, Inc. )), Light-colored resins, both aliphatic and aromatic (Hercolite®, Hercules Inc.), 'hydrogenated pure aromatic resins (Regalrez®, Hercules,' Inc.), hydrogenated mixed aromatic resins (Regalite®, Hercules , Inc.), aromatic resins (Picco®, Piccodiene®, Piccovar⑧ AP, and Picecvar® L (Hercules, 14) This paper size applies to China National Standard (CNS) A4 (2IOX 297 mm) (Please read the back (Please fill in this page again)

593499 A7 — ~ ____ B7 V. Description of the invention (12) -— he ·)), Plccolyte⑧a, picc〇lyte (g) c and P like olyte ⑧ S (Hercules, Inc ·), g Resin (Foral (R), Cardiac%, Escorez (I) line (Exχ〇η Chemical) and Wingtack (Eastman Chemical) line. The above list is for example only, not the entire I list. Know well Those skilled in the art can easily choose other adhesives. The wet COF of a field compound plus a COFE substance is greater than the compound when used alone, which will produce COF? Good support, especially for wet concrete improvement. For specific applications such as industry With regard to the soles of work boots, a wet COF of 〇4 or better is preferred. A wet COF of 0.3 or above, especially 0.35 or above, is very suitable for other applications (such as golf equipment, handles, Tennis rackets, squash rackets, and other sporting goods). The composition of the present invention can be used with fillers (reinforced) based on the amount of about 0-70 pbw (based on 100 parts by weight of EA0 polymer and cp〇 total weight). Sexual, non-reinforcing, or both). Add a pigment. Suitable for fillers and reinforcements, such as glass, oxidized stone, carbon black, metal salts such as carbonic acid and metal sulfates, such as calcium sulfate, metal oxides, such as magnesium oxide and zinc oxide, Talc, clay and graphite filler. Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs (please read the precautions on the back before filling out this page). Various customary additives can be used in the composition of the present invention. The additives include antioxidants, Surface tension modifiers, anti-caking agents, lubricants, anti-biocides' such as organometals, isotexone, organic sulfur and thiols // /; oxidants such as phenols, secondary amines, Phosphite and thioesters; antistatic agents such as quaternary ammonium compounds, amines and ethoxylated, propoxylated or glycerol compounds; hydrolytic stabilizers; lubricants, such as fatty acids, ________-15 -This paper size applies to 593499 Central Standard of Ministry of Economics, A7, B7, and B7. V. Description of the invention (13) Fatty alcohols, esters, fatty amines, metal stearate, Waxes and microcrystalline piers, polysecond oxygens and orthophosphates; release agents, such as fine or powdery solids, color, levitation, polysiloxanes, polyethylene glycols, and composite esters, such as Trimethylolpropane tristearate or pentaerythritol tetrastearate; pigments, dyes, and colorants; plasticizers such as the esters of divalent acids (or their anhydrides) and monohydric alcohols' such as o Acid esters, adipic acid esters and benzoic acid esters; thermal stabilizers, such as thiol organotin, octyl thioglycolate, and barium or cadmium citrate; UV stabilizers, hindered amines , O-Hydroxyphenylbenzotriazole, 2-¾yl, 4-alkoxybenzophenone, one. Salicylic acid ', one cyanoacrylate, one nickel chelator, and t malonic acid Fluorenyl esters and stilbenes. A preferred hindered phenol antioxidant is IrganoxTMi76 (ciba_Geigy Corp). If the above additives are used, the amount of each should not exceed 5%, based on the total weight of the composition. The composition of the present invention can be made into parts, plates or other forms using the method for treating elastomers. The composition may also be formed, drawn into a film, a multilayer laminate or a known board, or it may be combined with one or more organic or inorganic substances on any machine suitable for combination use. The elastomer composition of the present invention has a continuous or co-continuous phase formed from CPO. Compared with the composition made from the same component but with a continuous phase of EA0, the composition that does not have a COFE material or a related wet COF strengthening treatment has amazing properties, especially abrasion resistance (ASTMD 1630-83, NBS Abrader). '/, / Adding a COFE material to the composition results in a lower abrasion resistance than the COFE-free material &lt; composition. Similarly, it has -16 (210X297 mm) after specific processing conditions (please read the precautions on the back before filling this page)

593499 Μ B7 V. Description of the invention (14) The elastomer composition with improved wet COF will also lose some abrasion resistance. Surprisingly, however, the rolled edge tear strength (measured in accordance with the Footwear Institute of America test method serial number FIA-326, measured in pounds per pound per straight line) was not negatively affected by these processing conditions. The method for preparing the elastomer composition of the present invention includes treating a combination of a CPO, an elastic EAO, a plasticizer, and optionally a COFE material at a temperature, shear and pressure conditions sufficient to form a two-phase blended composition. . The amounts of the CPO, EAO, plasticizer, and COF'E materials and various substances are as described above. The CPO phase of the two-phase blend is co-continuous with the EAO. Polymer phase. The temperature, shear and lesser pressure conditions are sufficient to transform the CPO and EA0 into a molten state, and the molten CPO and EAO are at least partially intermixed with each other. Although any conventional melt processing equipment can be used, extruders, especially twin screw extruders, provide the desired results. Printed by the Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs (please read the precautions on the back before filling this page). Those skilled in the art understand that the temperature, shear and pressure conditions of each melt processing device are different. For example, when using a 30mm twin-screw extruder instead of a 90mm twin-screw extruder, the temperature setting in the barrel of the 30mm extruder and the extrusion screw rpm are set higher than the 90mm extruder to achieve a comparable result. Those skilled in the art can easily determine changes in these settings to meet requirements without unnecessary experimentation. The following examples and comparative examples can be used as indicators for such measurement. Without the use of COFE ^ t, the process for preparing a modified wet COF · <two-phase blended composition includes two steps>. In one step, the EA0 and CP0 are subjected to temperature, shear and pressure conditions sufficient to form the first melt blending composition. In step two, the composition is collected by 0, and the paper size is -17-. This paper size is in accordance with Chinese Gardener's Standard (CNS) A4 specification (2lOX 297 mm) 593499 A7 B7 5. The invention description (15) is converted into a pellet or Others are suitable for feeding form, and then feed it to the second melting processing device, where it returns to a molten state. In another step two, the composition can be directly fed to the second melting processing device, a recovery step is not required, and the molten state is maintained. In each case, when the first molten blend composition is moved to the second step in a molten state, a plasticizer is added to the first molten blend composition. With this variation method, the wet COF of the two-phase composition is formed to exceed the wet COF of the two-phase composition prepared by a single treatment of the CPO, EAO, and plasticizer through the same melt processing device. Under essentially the same equipment, it is better for the method to vary the temperature, shear and (if appropriate) pressure used in each device. The condition combination of the 30 mm twin-screw wiper is that the screw speed of the extruder is 400 rpm, and the temperature in the barrel is set enough to provide a polymer melting temperature of 2 3 3 0 ° C. As mentioned above, if the type and size of the device changes, the operating parameters need to be changed appropriately. Confirmation of continuous or co-continuous phases can be easily performed via TEM. This technique involves the cryosectioning of a sample. The surface of the specimen section was then stained (exposed to steam) with a 0.5 wt% ruthenium tetraoxide solution. The samples were then examined using Ding M (JEOL 2000FX) and photographed. This magnification is usually set to &gt; 7,500X. Printed by the Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs (Please read the notes on the back before filling out this page) The following examples demonstrate the improved abrasion resistance of the representative composition of the present invention. Compared with the formulated polyvinyl chloride and styrene block copolymers, the elastomer composition also has improved thermal rubber strength (also known as "mold curing"), which is based on dynamic mechanical spectroscopy ( &quot; DMS &quot;) measurement. / It is generally believed that the composition of the present invention also provides improved thermomechanical properties at high temperatures (e.g., 100-120 ° C), such as in load tests and other thermomechanical analyses. -18- The size of this paper is applicable to Chinese National Standard Plum (CNS) A4 (2l0x 297mm) Μ B7 V. Description of the invention (16 The following examples illustrate but do not understand the type pull-Λ white or dark restrictions Unless otherwise stated, all parts and percentages are stated (please read the notes on the back before filling out this page). The percentages of poverty, knife and knife are based on weight, which is based on the total weight. The Arabic numerals indicate the beta case (Ex), and the letters indicate the comparative man (Comp Ex). The following table! Provides information on the physical properties of various materials used to prepare the compositions of the examples and comparative examples. ΕΑ0] to εα 〇_6 Preparation or speaking from

DuPont Dow Elastomers L LC, HR 丄 丄, and EAO-7 and EA0-8 were purchased from

The Dow Chemical Company o EAO-i is an EO polymer (Lengage (§) 8 i 80) having an L of 0.5 g / 10 minutes and a density of 0.3 g / cm3. ΕΑ〇 · 2 is an evolved acetamidine / propylene / ethylene probenbornene (ENEB) polymer with an ENβ content of 5%. EA0-3 is an evolved ethylene / propane / ενβ polymer with a £ NB content of 0.5%. ΕΑΟ-4 is an ethylene / propylene η, 4-hexadiene polymer (Nordel® 24 7 0) 'which has a 1,4-hexadiene content of 6.00 / 0. ΕΑΟ-5 is an experimental EO polymer printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs. It has a Muni viscosity (MLi + 4 of 70) and a density of 0.87 g / cm3. EA0-6 is a polymer Ethylene hydrocarbon elastomer (POE) (Engage® 8842), 12 of which is 1 g / 1 () minutes and density is 0858 g / cm3. EAO-7 is a linear low density polyethylene (LLDPE) (Dowlex⑧ IP-90). EAO-8 is also LLDPE (Dowlex⑧ IP-60) 〇PP-1 is a PP homopolymer (Proxifax 6323, Himont). PP-2 is a PP homopolymer (PD 701, Himont ). PP J is a 4 PP homopolymer r (Valtec⑧ HH 444, Himont) 〇PI -1 is a kind of high dryness stone sacrificial oil (Sunpar® 2Ϊ80, Sun Oil Co.) 〇-19 This paper is applicable to China National Standard (CNS) A4 Specification (2l0X 297 mm) 593499 Five A7 ~ ____ B7 'Invention Note (17) ~ —

Pl-2 is a low viscosity paraffin oil (Tllfflo® 10, Lyondell Co.). Fi_i is a kaolin clay filler with a surface treated and calcined (Translink⑧ 37, Engelhard) 〇Vess in poise (vise) 値 Measured from the curve of the logarithm of the shear rate versus the logarithm of the particle size, the curve is used An instrument, such as that sold by Rhometric Instrument, is made by dynamic spectroscopy. As shown in Table I, the viscosity 値 is 200 sec-1, using a 25 millimeter (mm) parallel plate at a cut rate of 200 ° C. The Mone Viscosity (MV) of EA0 polymer (ML1 + 4 at 125 ° C) and the melt flow rate (MFr) (g / 10 min) of PP polymer at a load of 2.16 kg at 23 0 ° C help to show Characteristics of raw materials. (Please read the notes on the back before filling this page)

-1T Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs I Component / Properties MWD MV MFR (g / 10 minutes) Viscosity (poise) EA0-1 2.1 25 — 14000 EA0-2 2.2 26 — 17000 EA0-3 4.3 70 — 21000 EA0-4 3.5 70 — 21000 EA0-5 2.02 70 — 21000 PP-1 3.4 '-12 3000 PP-2 3.6 — 35 /' / 1900 PP-3 — — 70 1300 One means not measured -20- present Paper size applies to China National Standard (CNS) A4 (210X 297 mm) 593499 5. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 〇inp A7 B7 Invention Description (18

EX1-7 and COMP EX A and B. Nine sample compositions (Ex i-7 and c Ex A and Β) were prepared from the combinations shown in Table II.

Table II

Ex / Comp Ex No. EAO PP PI Fi (wt%) Viscosity ratio-ID% ID% ID% A 1 41 1 21 '1 38 0 6.1 B 2 41 1 21_ 1 38 0 ^^^ 7.1 1 1 42 3 23 1 35 0 11 to 2 2 42 3 23 1 35 0 13 3 2 42 2 23 1 35 0 9 4 3 42 2 23 1 35 0 11 5 3 44 2 18 2 37 1 11 6 4 43 2 19 2 37 1 11 7 氺 42.35 2 15.7 2 41 0.95 11 * Means a composition of 35.6% EAO-5, 5% EAO-6, and 1.75% EAO-8. 0 Examples 1-4 and Comparative Examples AB are based on 卩, type laboratory scale The Fari '// j Farrell Banbury Mixer. For each example and comparative example, the EAO polymer was added at 130 ° C and melted for two minutes V 'at a rotation speed of 80 revolutions per minute (rpm) and then -21 sheets in two minutes Applicable Chinese National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling out this page j

593499 A7 B7 V. Description of the invention (19) Add plasticizer and continuously stir it. The pp polymer was then added to the mixer, and radon gas was added to increase the temperature, and the rotation speed was increased to ′ 丨 rpm. After four minutes, the contents of the mixer were removed, rolled into a plate, and then ground to serve as an injection molded test specimen. Examples 5 and 6 were prepared using a ZSK 30 mm Werner and Pfluderer co-rotating twin screw extruder. The epsilon polymer, the PP polymer, and the filler were blended and dried'in a drum blender before being added to the extruder using a calibrated feeder. The blender was operated at 2000 rpm to effectively melt the dry pellets and provide a molding pressure of 300 pounds per square inch (psi) (2070 kilo-bascars (kPa)). Number! The _ 5 zone is set to 140 ° C, 110 ° C _, 1 70 ° C, 180 ° C, and 190 ° C, and the extrusion die is set to 1 90 ° C. This plasticizer was added to zone 2 of the press using a calibration pump and an injection nozzle. The extrudate discharged from the extruder was quenched in a water tank (13 ° C) through a double-strand die. The extrudate was discharged from the water tank, dried with an air knife, and then granulated. • Example 7 was prepared using the same device as in Examples 5 and 6, but the extruder was operated at 240 rpm instead of 200 rpm, and different temperature settings were used. For extruded materials that pass through the extruder for the first time without the addition of plasticizers, the temperature settings in zones -1-5 are 150 ° C, 165 X :, 185 ° C, 185 ° C, and 185 ° C, the temperature of the extrusion die is 180 ° C. For the second pass through the extruder and the addition of plasticizers in zone 2 all temperatures are f; i 'is set to 175 ° c. After the second pass, the extruded product was treated as in Example 5-6 '. Each of the objects of Examples 1-7 and Comparative Example AB was made into injection molding. -22- This paper's standard is applicable to China National Standards (CNS) A4 (210X29 * 7mm) (Please read first Note on the back, please fill in this page to pretend · 11, the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs of the People's Republic of China 593499 A7 B7 V. Description of the invention (2) Sample or porcelain flower metal plate s, with an area of 154.8 square centimeters (cm2 ), The thickness is 0.312 cm. The porcelain flower metal plate s is a reciprocating screw injection molding machine (30 mm screw) using an Arburg type 3 70C-800-225 (800 thousand Newton (kN) hydraulic clamp). ) Preparation, set the barrel temperature in a predetermined way, the first barrel zone is 12 1 ° C, then the subsequent zones are 177 ° C, 196 ° C, and 204 ° C, and the nozzle is set to 1 85 ° C. Although porcelain flower metal The mold temperature is set to 8 t, but it is usually 2 1 ° C during the molding period. The screw angular velocity, injection pressure and holding pressure are 30 m / min, 400-700 bar &lt; (40 -70 megapascals (MPa)) and 30 bar (3 MPa). During the injection molding from 1.9 to 2.1, the standard injection volume of each porcelain flower metal plate s is 80 square meters. Min. The mold settling time is 2 0-30 seconds. The sample is tested for physical properties to determine NBS abrasion resistance (ASTM D-163 0), tensile strength at break (psi / kPa), and break Percentage of extension (%). The physical properties are shown in the table below. Use NBS friction 〇 ー ー 〇 father father rubber (NB S reference material) for comparison. (Please read the precautions on the back before filling this page ) &gt; Printed by the Consumers' Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs 23-593499 A7 B7 V. Description of Invention (21)

Table III Ex / Comp Ex Viscosity Ratio NBS Friction / rupture Tensile strength (psi / MPa) Fracture elongation (%) A 6.1 33 900 / 6.2 820 B 7.4 38 780 / 5.4 640 1 11 81 940 / 6.5 730 2 13 88, 660 / 4.6 7 510 3 9 98 740 / 5.1 610 4 11 117 -750 / 5.2 530 5 11 121 660 / 4.6 670 6 11 118 590 / 4.1 560 7 11 92 670 680 Reference N / A 100 N / AN / A (Please read the notes on the back before filling this page) The information shown in Table III printed by the staff of the Central Bureau of Standards of the Ministry of Economic Affairs and Cooperatives proves that the composition with a viscosity ratio of 9 or more has better abrasion resistance than a viscosity ratio. For low composition, see, for example, Comparative Example A and Example 1. Similar results are expected for compositions with EAO polymers, CPOs and plasticizers, and where appropriate, such as the fillers, pigments, and stabilizers described above. Using the DMS of Rheometric Scientific to measure the temperature at 130 ° C, the storage modulus of the '/' j compound (8 mm parallel 'plate) can reveal the strength of the raw rubber. The storage modulus of Example 6 is 789,000 dynes / cm 2 (8 137 kg / m 2). Polychlorinated propylene combination-24- This paper applies Chinese national standard (CNS) A4 specifications (210X 297 mm) A7 A7 B7 Invention description (22 (please read the precautions on the back before filling this page)) and ^ ethylene block copolymer composition (both are usually used to make boots The pillars of the column body ~ Shichang, / mesh, Example A have a storage modulus of 598,000 dyne / cm2 (6098 m) nj, 000 dyne / cm2 (1764 kg / m2) and less than 5,000 dyne C ^ S 1 1 2 (g / m) ° These data show that the composition of the present invention is far superior to commercially available materials, and that it provides significant improvements for similar compositions with lower viscosity ratios. It is expected that other compositions representing the present invention will have similar As a result, Examples 8-12 and Comparative Example c were prepared using the procedures and rewards of Examples 5-6 and preparing Examples 8 and 9, but the temperatures of the 15th zone and the extrusion module were 140. (: , 160 ° C, 165 ° C, 170C, 165C, and 160 ° C. The compositions of Examples 8-9 are shown in the table below. Haake 9000 double screw with cooling water tank was used Rod Extruder Preparation Examples 10-12. Zones 1-5 and 6 (the extrusion die) were set to 140 ° C, i60 ° C, 170 ° C, 17CTC, 160 ° C, and 150, respectively. : Example 10 Human Π is 100 pbw of the composition of Examples 8 and 9 and 10 pbw C 0 FE -1. Example 12 is a 100 pbw Example 8 and 10 pbw COFE-2 Composition. If the cofe compound is present, it is dry blended with the composition before melt processing using the extruder. Comparative Example C is injection molded according to the foregoing. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs? Table Comparative Example C is a phenethylfluorene-butadiene-styrene compound (SBS-1) 'Sometimes used as shoes, sold by A-WCompounding Ltd., quotation-TR2 046. Reinforced as COF COFE-1 of the compound is Regalite® S 101, an adhesive (hydrogenated 7-mixed aromatic resin) sold by Hercules, Inc. COFE-2 is an evolutionary EO polymer (DuPont Dow Elastomers LLC), which has two Modular MWt) '(50% of 200,000 Mw 25- This paper size applies to China National Standard (CNS)) (21〇X 297 mm) Description of the invention (23 A7 B7 gold degree is 0.867 g / litre ^ 10,000 cm, and 50% of 12,000 Mw, close shoulder is 0.862 g / cm ^, the overall density of, ^ is 0.865 g / cm ^ 3, and M is 3.0 G / 10 minutes).

PP-2 15.68 17.01 F Bu 1 0.94 1.01 EAO-7 1.74 1.89 P1-2 41.0 36.0 (Please read the precautions on the back before filling out this page "-Order by the Central Bureau of Standards of the Ministry of Economy Procedures and devices of 1-7 The compositions of Examples 8-12 and Comparative Example C were made into injection-molded test ceramic flower metal plates.... The injection molding processability was improved during the manufacture of the test flower metal plates. The particle size and screw position of the injection molding switched to the maintained state are adjusted at the highest estimated speed, making the slot mold almost impossible to full. The temperature of the injection molding device • • Zone 1 (feeding zone) feed temperature is 250 Τ (121 × :), the second zone is 35 ° (177 C), the third zone is 3 85 ° C (196 ° C), the fourth zone is 400 Τ (204), and the fifth zone is 3 85 ° (丨 96 〇. Remember the green injection molding speed shoulders (5, 8, 5, 5, 20, 30, 50, and 70 cubic centimeters / second to fill the slot mold time and peak injection pressure. The corresponding surface shear rate in the flow channel ( See the performance of the peak injection molding pressure. The surface shear rate is using the injection molding-26- ^ 93499

Degree and molding physical size calculation. The sharp injection pressure (see Table VI) attributed to the setting of the injection speed is used as an index of processability, because it depends on the processing reaction depending on the melt viscosity, injection speed, and forward cure rate. Heat injection molding technicians understand that the injection pressure is calculated by the tonnage of the plywood of the molding machine. It is also said that the self-failed injection molding resin will produce excessively high plywood pressure before filling the molding cavity at the highest particle melting temperature. Flashover occurs when the peak pressure exceeds the plywood pressure. Therefore, compounds with a lower injection pressure at a given injection speed (shear rate) are considered to be easier to process. The physical properties of the test porcelain plates of representative examples 8-12 and comparative solid scrape C were analyzed, and the wet and dry stones were tested. The bricks Cof, NBS abrasion resistance, DIN abrasion resistance, hardness (Xiao Ear A) and injection molding viscosity at eight different shear rates. The coefficient of abrasion (COF) test is performed using stone bricks (dry or hydrated) in accordance with ASTM D-1 894. The NBS abrasion resistance was measured in the same manner as in Example 7. DIN abrasiveness (measurement of volume loss) is determined according to the din 535 16 test method. The hardness (Shore A) test is performed according to ASTM D-2240. The physical property test data is summarized in Table V below.

Form V (Please read the notes on the back before filling out this page)

, 1T Consumers' Cooperatives, Central Standards Bureau, Ministry of Economic Affairs, India

Ex No / Properties 8 9 10 11 12 C Dry COF '0.39 0.39 0.9Γ 0.70 0.52 0.5 Wet COF ， 0.27 0.27 0.57' 0.48 0.36 0.48 NBS grinding property 90 99 56 74 77 76 DIN abrasiveness (cubic millimeter) 144 133 238,, 184 159 293 Hardness (Xiaoer A) 61 68 56 61 60 73 __27_ This paper size applies to China National Standard (CNS) A4 specification (2: 0X 297 mm) 593499

AB V. Description of the invention (25) Table VI Ex / Comp Ex 8 9 10 11 12 CP (psi / MPa) @ 22289 s'1 9619 / 66.3 10829 /74.7 7833 / 54.0 8746 / 60.3 9584 / 66.1 8744 / 60.3 P ( psi / MPa) @ 15921 s &quot; 1 7747 / 53.4 8856 / 61.1 6290 / 43.4 7174 / 49.5 7629 / 52.6 7186 / 49.5 P (psi / MPa) @ 9552 s1 6221 / 42.9 7272 / 50.1 4982 / 34.3 5777 / 39.8 6130 / 42.3 6246 / 43.1 P (psi / MPa) @ 6368 s'1 5515 / 38.0 6538 / 45.1 4364 / 30.1 5189 / 35.8 5527 / 38.1 5834 / 40.2 P (psi / MPa) @ 4776 s'1 5170 / 35.6 6134 /42.3 4247 / 29.3 4939 / 34.1 5277 / 36.4 5628 / 38.8 P (psi / MPa) @ 3184 s &quot; 1 4896 / 33.8 5861 / 40.4 3997 / 27.6 4762 / 32.8 5101 / 35.2 5628 / 38.8 P (psi / MPa) @ 2547 s_1 4752 / 32.8 5688 / 39.2 — 4689 / 32.3 4954 / 34.2 5746 / 39.6 P (psi / MPa) @ 1592 s_1 4466 / 30.8 5602 / 38.6 3938 / 27.2 4659 / 32.1 4969 / 34.3 6143 / 42.4-means not measured (Please read the precautions on the back before filling this page) The information indicated in the printed form V of the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs indicates that the addition of a COFE material will increase the wet COF, but it will not have a negative impact on the physical properties . COFE-2 with only a 50 wt% low molecular weight portion is effective to provide a 5 wt% COF reinforced compound. If the amount of the COFE-.2 is doubled (as shown in Example '15), the further improvement of the wet COF is more obvious. If COFE-2 replaces at least part of EA0-6, it is still expected that the wet COE can be further strengthened. The data shown in Table VI indicate the addition of COF compounds to this compound. -28- Gage 4 Λ Ns lQ

Cm 7 7 2 X 593499

A B V. Description of the Invention (27) The data of the embodiment 14 is between those of the embodiments 9 and 11.

Table VII

Ex No / Properties 13 14 15 16 17 Dry COF 0.41 0.52 0.57 0.64 0.77 Wet COF 0.32 0.36 0.39 0.41 0.45 NBS Abrasiveness 86 102 — — — DIN Abrasion (Cubic Millimeter) 7 154 138 — — — Hardness (Shore A) 57-one 64 59 59 56 one means not measured-

Table VIII (Read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs

Ex / Comp Ex 15 16 17 Temp (° F / ° C) for P Test 365/185 365/185 365/185, P (psi / MPa) @ 22289 s'1 10067 / 69.4 8524 / 58.8 8127 / 56.0 P ( psi / MPa) @ 15921 s'1 7966 / 54.9 6790 / 46.8 6378 / 44.0 P (psi / MPa) @ 9552 s &quot; 1 6540 / 45.1 5437 / 37.5 5040 / 34.7 P (psi / MPa) @ 6368 s'1 5952 /41.0 4952 / 34.1 4541 / 31.3 P (psi / MPa) @ 4776 s'1 ^ 5672 / 39.1 4688 / 32.3 4305 / 29.7 P (psi / MPa) @ 3184 s'1 5408 / 37.3 4364 / 30.1 / i 4086 / 28.2 P (psi / MPa) @ 2547 s'1 5334 / 36.8 4306 / 29.7 4041 / 27.9 P (psi / MPa) @ 1592 s'1 5364 / 37.0 4262 / 29.4 3982 / 27.5 -30- This paper size applies to China Standard (CNS) present (210X297 mm) 593499 Printed by the Central Consumers Bureau of the Ministry of Economic Affairs, Consumer Cooperatives 31-A7 B7 V. Description of the invention (28) The information shown in Tables VII and VIII shows the changes in the adhesive level and the different adhesives. The effect of improving the wet cOF of the polymer compositions of Examples 13-17 was improved. Specific adhesives and specific amounts provide higher COF improvements than otherwise. It is expected that similar results will be obtained with the other polymers, polymer compositions, gums (whether conventional or low MW polymers) and additives described above. It is known in the art that suitable compositions and adhesives can be easily selected, as well as the amount of various components necessary to achieve the desired wet COF. Example 1 8 -1 9 and Comparative Example D 1 use 60.3% EA0-4, 26.6% PP-2, 8.5% EA0-6, 2.9% EA0-8, 1.6% Fi-1 and 0.1% Irganox ® 1076 (Hindered Phenol Antioxidant, Ciba-Geigy Corp) Composition Another example and a comparative example were prepared. The composition was subjected to three different sets of processing conditions. For all three conditions, a 9.0-meter Berstorff twin screw extruder was used instead of the 30 mm twin screw extruder of Examples 5-6. Zones 1-6, the sieve changing body, the transition zone and the shooting mode were set to 490 T (254.4 ° C), 440 Έ (226.7. (:), 545 down (285 · 0 ° 0, 500 down (260.0). 〇, 400 T (204.4 ° C), 590 T (310.0 °, 420 ° (215.6 °, 425 ° (218.3 °, and 450 ° (23 2.2 ° C)). The extruder was at 25 ° rpm with the above. The temperature combination operation effectively produced a polymer with a melting temperature of 43 ° T (221 ″.). —. A water bottom granulator converts the melted polymer into pellets. Comparative Example D The composition of the press. Example 18 was used to feed the same composition into the extruder, but in the third area> the king used a sufficient amount of P1-2 to improve the procedure used in Comparative Example D. A paper size suitable for home finance (CNS) (Please read the notes on the back before filling this page)

593499 A7 B7 V. Description of the invention (29) The final product with a plasticizer content of 41%. In Example 19, the pellets of Comparative Example D were added to the feed throat, and then the same amount of plasticizer as in Example 18 was added in the third zone. The composition of Examples 18-19 was converted into the injection-molded test porcelain plate as in Example 1-7, and then the physical properties of Example 8-12 were analyzed. The burr tear strength is measured in accordance with Footwear Institute of America Test Method No. FIA-326 and is calculated in pounds per straight inch (pli). The physical property test data is summarized in Table 4 below. The peak injection molding pressures of Examples 18-19 and Comparative Example D were measured in the same manner as in Examples 8-12, and are shown in Table X below. — (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs IX Ex No / Properties 18 19 Dry COF (Stone Brick) 0. 39 0.61 Wet COF (Stone Brick) 0.27 0.43 Dry COF (painted wood) 1.45 1.72 Wet COF (painted wood) 0.91 1.45 Dry COF (vinyl brick) 1.48 1.77 Wet COF (vinyl brick) 1.32 1.59 NBS abrasiveness 90 66 DIN abrasiveness (cubic millimeters) ) 140 208 Hardness (Shore A) 61 / / 59 / 'Melt Index (12) 7 38 Trimmed Edge Tear Strength (pli) 192 190', -32-This paper size applies to China National Standard (CNS) A4 (210X 297 mm) 593499

7 B V. Description of the invention (30) Table X Ex / Comp Ex 18 19 D Temp (° F / ° C) for P Test 365/185 365/185 365/185 P (psi / MPa) @ 22289 s &quot; 1 7819 /53.9 7495 / 51.7 16636 / 114.7 P (psi / MPa) @ 15921 s'1 6264 / 43.2 5790 / 39.9 14196 / 97.9 P (psi / MPa) @ 9552 s'1 5040 / 34.7 4409 / 30.4 12080 / 83.8 P ( (psi / MPa) @ 6368 s_1 4507 / 31.1? 3703 / 25.5 11095 / 76.5 P (psi / MPa) @ 4776 s'1 4277 / 29.5 3410 / 23.5 10625 / 73.3 P (psi / MPa) @ 3184 s_1 4090 / 28r2 3086 /21.3 10199 / 70.3 P (psi / MPa) @ 2547 s &quot; 1 4003 / 27.6 2969 / 20.5 10228 / 70.5 P (psi / MPa) @ 1592 s &quot; 1 3931 / 27.1 2792 / 19.2 9993 / 68.9 (Please read the back first Please note this page before filling in this page) Printed by the Central Bureau of Standards of the Ministry of Economic Affairs-Industrial Consumer Cooperatives. First, the data in Table X show that for a given combination of substances, the two treatment procedures (Example 19) provide better flow characteristics than the one treatment procedure (Example 18). Second, the data in Table X show that the beneficial effect includes a plasticizer. Controls without plasticizers Example D and Examples 18 and 19 with plasticizers. Third, the information in Table IX shows that the improvement of wet COF (stone brick) is accompanied by a decrease in abrasion resistance. Surprisingly, however, the burr tear strength remained almost constant. It is expected that all of the other compositions and treatments described above will yield similar results. Those skilled in the art can easily select processing conditions to provide the desired balance between flow properties and wet / COF and / wear resistance. / Examples 20-22, '' * Treat the composition of Comparative Example D as in Examples 5-6, but do not apply -33- This paper size applies the Chinese National Standard (CNS) Λ4 specification (210X 297 mm) 593499 A7 _____ B7 __ 5. Description of the invention (31) The extrusion screw speed of the 30 mm twin screw extruder is increased to 400 rpm, and the uniform barrel temperature settings are used: 280 ° C (Ex20), 3 10 ° C (Ex21 ) And 33 0 ° C (Ex22). This setting provides 302 ° C, 335 ° C, and 356, respectively. (: The polymer melting temperature. The injection molding test data of Examples and Comparative Examples D are shown in Table XI.

Table XI

Ex / Comp Ex 20 21 22 D Temp (° F / ° C) for P Test 365/185 365/185 365/185 365/185 P (psi / MPa) @ 22289 s_1 19375 / 133.6 18757 / 129.3 16563 / 114.2 16636 /114.7 P (psi / MPa) @ 15921 s'1 17067 / 117.7 16420 / 113.2 14281 / 98.5 14196 / 97.9 P (psi / MPa) @ 9552 s &quot; 1 15156 / 104.5 14230 / 98.1 12326 / 85.0 12080 / 83.3 P ( psi / MPa) @ 6368 s'1 14288 / 98.5 13304 / 91.7 11370 / 76.5 11095 / 76.5 P (psi / MPa) @ 4776 s &quot; 1 13965 / 78.4 12804 / 88.3 10889 / 75.1 10625 / 73.3 P (psi / MPa) @ 3184 s &quot; 1 13612 / 93.9 12407 / 85.5 10507 / 72.4 10199 / 70.3 P (psi / MPa) @ 2547 s &quot; 1 13524 / 93.2 12260 / 84.5 10319 / 71.1 10228 / 70.5 P (psi / MPa) @ 1592 s' 1 13568 / 93.5 12399 / 86.6 10452 / 72.1 9993 / 68.9 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) The information shown in Table XI shows that when the melting processing device is changed, Equivalent results of changes in device parameters required. The information of Example 22 is similar to that of Comparative Example D. In order to obtain such information, the melting temperature of the 30 mm double 纟 tired rod 'extrusion 碜' must be 330 ° C. As in Examples 18 and 19, the addition of plasticizers caused a sharp drop in the peak pressure measurement standard. It is expected that similar results may be obtained for other compositions and processing conditions disclosed herein. ， -34- ^ The paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (2) 0 × 297 mm. Application date No. Mou 17103335 (The above items will be filled in by the Bureau) ITm if

Elastomer composition, preparation method and application thereof------ ~ -_

A correction i charge 593499 Chinese manual revision page (February 91) Patent specification, $! Name English

ELASTOMERIC COMPOSITION AND ITS PROCESS OR PREPARATION AND USE Name Nationality l. Morgan Markhuf 3. Michael Francis Martin 5. Dipasparek is the United States and Europe 2. Laura Ballvieve 4. McConney Slano people living and domicile 1. No.708 Milton Street, Anglanton, Texas, USA 2 59 North Carrley Avenue, Lake Jackson, Texas, USA 3. Wat Ai, Lake Jackson, Texas, USA Li Street 丨 0 No. 3 4 · North Jackson Road, Lake Jackson, Texas, USA 丨 403 No. 5 · 59 North Cui Li Avenue, Lake Jackson, Texas, USA Name (Name) Nationality American DuPont Ceramic Elastomer Company USA 3 The applicant lives in Dan R. Howard Julia Shaw, No. 300 Bellerview, Wilmington, Delaware, USA. The paper size is applicable to China National Standards (CNS) A4 (21〇X 297 mm) 593499.

Patent Application No. 87103335. Revised Page of Chinese Specification (February 91) 5. Description of Invention (6) / Dimer Monomer (EPDM) Copolymer. More detailed examples include homogeneously branched, linear EAO copolymers (such as Tafmer ™ manufactured by Mitsui Petro Chemicals Company Limited and Exact ™ manufactured by Exxon Chemical Company), homogeneously branched and substantially linear EAO Polymers (eg Affinity ™ polymers sold by Dow Chemical Company are Engage® polyolefin elastomers sold by DuPont Dow Elastomers LLC, and Nordel® and Nordel® IP hydrocarbon rubbers sold by DuPont Dow Elastomers LLC ( EPDM copolymer). A better EAO polymer density (measured according to aSTM D-792) is 0.85-0.88 g / cm3, especially 0.85-0.87 g / cm3. The EAO polymer must have at least one of the following One (a) a viscosity measured at 200 ° C and a cutting rate of 200 sec · 1, which is at least nine times the viscosity of the crystalline polyolefin, (b) at least (2) a Muni viscosity of 20 ( ML1 + 4) at 125 ° C, and (c) molecular weight distribution (MW / MN) 2 2.0. The MW / MN is preferably from 2-5, and more preferably from 2-4. The Muni viscosity is 2 50. Good, &gt; 70 is better. The upper limit of the viscosity of the muni Fixed, not absolute months, of the original processing limitations of the equipment used to make the composition of the present invention. "Substantially linear" means that the polymer's backbone is replaced by 0.01 to 3 per 1,000 carbon atoms. Long-chain branching substitution. Long-bond branching or LCB means the slit length exceeding short bonds, which is formed by the combination of heart-linked smoke and EAO polymer or EAO polymer. If the chain length is greater than six carbon atoms, Although the carbon-13 nuclear magnetic resonance (C13 NMR) spectrum cannot distinguish or measure the exact number of anti-prime atoms in the S bond, the presence of LCB can be measured, or at least estimated, from the ΑΑΟ polymer MWD. From the melt flow Rate (mfr) -9-This paper size applies to Chinese National Standard (CNS) specifications (210 X 297 mm) 593499

Patent Application No. 87103335 (Chinese version) (August 91) A7 ___ B7 V. Description of the invention (9) 晞 fe elastomer and other polymers made by CGC. Suitable CPs include copolymers of pp homopolymer and propylene with an α-associated hydrocarbon such as acetamidine, 1-butanefluorene, 1-hexene, or 4-methyl-pentene, or a homopolymer with A blend of copolymers. The α-olefin is preferably ethylene. The co-permanent may be a canonical copolymer or a block copolymer, or a blend of a random copolymer and a subsequent copolymer. Therefore, this component is preferably selected from the group consisting of ρρ homopolymers and P / E copolymers. This component has at least (approximately at least ug / 10 minutes of MFR (23 ° C and 2.16 kg weight), preferably 220 g / 10 minutes, and (b) one of MW / MN 2 2.0. MFR of The upper limit is 200 g / 10 minutes. The preparation of PP homopolymer and P / E copolymer also involves the use of Segler catalyst,

i is used in combination with osmium dichloride and diethyl pentachloride I, as described by Cecchin in USP 4,177,160. The polymerization methods used to make pp include a slurry method, which is performed at 50-90C and 0.5-1.5 MPa (5-15 atm), and a gas-phase and liquid-phase method, where extra care must be taken when removing amorphous polymer. Ethylene can be added to the reaction 'to form a polypropylene and ethylene block. PP resins can also be prepared using any metallocene, single-site, forced geometry catalyst, and other related methods. Plasticizers suitable for the composition of the present invention are selected from alkyl esters including hydrocarbon oils and carboxylic acids. The hydrocarbon oil is preferably selected from naphthenic oils and paraffin oils. The alkyl group must have from 6 to 30 carbon atoms. Suitable carboxylic acids for preparing the esters include from 1 to 4 carboxylic acid carbon atoms. Exemplary esters include dioctyl azelate, monooctyl sebacate, and n-butyl glycerol. The plasticizer is present in an amount of 1-200 pbw, based on 100 pbw elastic ea〇 polymer. The content is preferably 20-200 pbw, 5 (M5〇pbw is _-12- This paper size applies Chinese National Standard (CNS) A * specifications (21〇χ 297 mm) 593499 Patent Application No. 87103335 λΊ (修正 Correction page of the Chinese manual (February 91) B7__ 5. Description of the invention (10) The composition of the present invention optionally includes a COFE material that strengthens wet COF. This material is also called a "wet COFE material", Its system (a) is selected from the group consisting of conventional adhesives and low molecular weight, low crystallinity polymers, molecular weight propylene copolymers, and (b) present in amounts greater than 0 pbw. Suitable low MW, low crystallinity polymers include EAO polymers, Especially for EO copolymers. When using C 0 FE material, the amount is based on the total weight of C P 0 and elastic EAO polymer per 100 pbw &gt; 0 to 40 pbw. The amount from &gt; 0 to 30 pbw is Better, from> 0 to 20 pbw. When the wet COFE material is a low molecular weight, low crystallinity polymer, the amount is sufficient to provide the composition with improved processability. The improved processability is related to an (1 ) Treated under the same processing conditions and (2) same but without COF The comparison of the composition of the E material is determined by its peak injection molding pressure reduction. The low MW, low crystallinity polymer also has significant characteristics. Low MW means the weight average molecular weight (MW) is 500-25,000. The MW is 500-20,000 is preferred, 500-15,000 is preferred. When the crystallinity &lt; 20% is considered low crystallinity, preferably from 0-1 5%, and more preferably from 0-10%. Tg of the low MW polymer It is also applicable in the range of -40 to -65 ° C. When the low MW, low crystallinity polymer is present in the composition of the present invention as a COFE material, it provides unexpected benefits and improves the processability of these compositions. It is proved that one of the improved processability methods is to compare the presence or absence of a low MW, low crystallinity polymer as a COFE material, and the peak injection molding pressure difference of the composition. It is sufficient to improve the wet COF of the composition- 13- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 593499 Patent Application No. 87103335 (Chinese version) Amendment Sheet (February 91) A7 B7 'k. V. Description of Invention (26: Positive-molded flow characteristics do not cause negative effects. Effectively reduce the relative amount of plasticizer in different places. Compared with the implementation: Compared with 9, 'Example 10 and u contain a cofe material 2 = object 8 has a modified flow characteristics. As mentioned above, at the same injection speed Note: 'Lower peak injection molding pressure during production clearly indicates improved flow characteristics (2: processability). In other words, certain compounds containing COFE are easier to injection-mold than equivalent compositions without two compounds. Examples 13-17 Examples 15-12 were prepared using the summary device and procedure of Example 10-12, and Examples 13-6 were prepared using the summary device and procedure of Example 5-6. Examples 13 and 14 repeat Examples 10 and u, respectively, but replaced 10 with ~ 5 COFE-1, and replaced 90 pbw of the composition of Examples 8 and 9 with 95, respectively. Example 15 Example 12 was repeated, but the composition of Example 8 was replaced with 80 and 90 pbw. The example repeats Example 10 with i7, but uses COFE_3 (Example 16) or cofe_4 (Example ⑺) instead of COFE-1. COFE-3 is an experimental low molecular weight (number average molecular weight (MN) is 9200) E) copolymer (Dupont D0w ε1_5 LLC ·) 'has a density of 0.870 g / cm3 and an effective MI of 1770 g / 10 min. COFE-4 is Hercotac® 1148 , A kind of

Adhesive for HerCUleS, InC. (Stone monomer, natural monomer, or a mixture of both, with a Tg of 44 C 'MW of 15,000 and MWD of 9). Table νπ and table viii show that the physical properties of Examples 13-17 and the peaks and pressures of Examples 13-17 are inaccurate. However, it is not shown that the peak injection molding pressure data of the expected embodiment 3 is between the values of the above-mentioned embodiments 8 and 1 (). Similarly, pre-29- this paper size applies Chinese National Standard (CNS) mm)

Claims (1)

593499 Patent Application No. 087103335 g Replacement of Chinese patent application scope (February 1993) Redundant, patent application scope ............... 1 、 -1 1 ... -• Factory r ..... ',' Jing ·, 1 1 1. An elastomer composition comprising: a. 20 to 50 parts by weight-based on the total weight of a and b-crystallinity Polyolefin, which is selected from the group consisting of polypropylene homopolymer and propylene / acetic copolymer, wherein the crystalline polyolefin has a melt flow rate of 12 g / 1 measured at a temperature of at least 2301 and a weight of 2.16 kg () Minutes to 100 grams / 10 minutes and (ii) molecular weight distribution (MW / MN) of one of 2.0 to 9.0; b · 80 to 50 parts by weight-based on the total weight of a and b-elastic ethylene / Alpha-olefin polymer with or without polymerized diene monomer therein, wherein the acetamidine / α-olefin polymer has a temperature of at least 200 ° C and measured at a shear rate of 20086 (^ 1) The viscosity is at least nine times greater than the crystalline polyfluorene, (ii) the Muni viscosity (ML1 + 4 at 125 ° C) is 20 to 200, and (iii) the molecular weight distribution (MW / MN) is 2.0 to 5.0 one of them C. 1 to 200 parts by weight-in terms of per 100 parts by weight of elastic polymer-a plasticizer selected from the group consisting of hydrocarbon oils and carboxylic acid alkyl esters, wherein the crystalline polymer The olefin and the acetamidine / α-fluorene polymer exist in two different phases. The crystalline polyfluorene phase system is at least co-continuous with the ethylene / α-olefin polymer phase. The composition's abrasion resistance (ASTM D163 0-83, NBS Abrader) is a similar composition that is larger than the same composition but has only a single continuous phase formed by the ethylene / α · fluorene polymer. 2. The composition according to item 1 of the scope of patent application, The ethylene / α-hydrocarbon polymer has a Muni viscosity of 70 to 200. 3. The composition according to any one of items 1 to 2 of the scope of patent application, in which the Chinese paper standard applies to the Chinese national standard (CNS) Α4 size (210X 297 mm) Patent application scope The ping / α-olefin polymer is a terpolymer of ^ local ethylene / α-associated hydrocarbon / difluorene monomer, and one percent is selected from the group consisting of raw ice &amp; 1, borneol-1, dicyclopentadiene, 1,4-hexadiene hydrazine di- or 5-ethylidene-2-orthobornadiene and mixtures thereof. • According to the scope of the applied patents 筮, 罘 1, ·, and 组合 composition, in which the ethoxylated / α-associated polymer has been dispersed in the form of α-olefin, the α- 晞; Fc contains 3-20 carbon atoms. According to the composition of claim i, the plasticizer is a hydrocarbon oil selected from the group consisting of naphthenic oils and paraffin oils. 6. The composition according to item i of the patent claim, further comprising a material, which is used in a range of 70 parts by weight based on the total weight of 玨 and b. The filler is selected from the group consisting of broken glass, Oxidation bites, carbon black, gold ^ carbonates, metal sulfates, metal oxides, talc, rhenium, and graphite fibers. 7. A composition according to item 丨 of the scope of patent application, which further comprises a house-free adhesive of 40 weight-in terms of &amp; and b per 100 parts by weight, a free adhesive, low molecular weight, low Crystalline polymers, low-molecular-weight ethylene / α-olefin polymers, and low-molecular-weight propylene copolymers provide a group of rhenium materials that provide higher coefficients of wet friction than those containing only five of the a, b, and c. Coefficient of friction, which is measured according to ASTM using a wet stele. 8. The composition according to item 7 of the scope of patent application, wherein the crystalline polymer has at least (a) a melt flow rate of 12 g / 10 measured at a temperature of 230 C and a weight of 2.16 kg Minutes to 100 g / 10 minutes and (b) the molecular weight distribution (MW / MN) is one of 2.0 to 9.0. -2- 593499 A8 B8 C8 _____ D8 2. Application scope of patent 9. The composition according to item 7 of the patent scope of Shenyin, wherein the acetamidine / α-gaki polymer has at least (a) a viscosity measured at a temperature of 190 ° C and a shear rate of 200 sec. Is at least nine times greater than crystalline polyfluorene, (b) the Muni viscosity (ML1 + 4 at 125C) is 20 to 200, and (c) the molecular weight fraction (MW / MN) is one of 2.0 to 5.0 10. The composition according to item 7 of the scope of patent application, wherein the COFE material is present in an amount greater than 0 parts by weight, and is the same as (1) receiving the same processing conditions and (2) the same composition but excluding the C0 FE material Comparison of the composition, when the wet COFE material is a low molecular weight, low crystallinity polymer, the amount is sufficient to improve the processability of the composition, which is measured with a sharp injection molding pressure reduction. 11 · A kind of preparation elasticity A method of forming a body composition, the method comprising subjecting a composition to temperature, shear and pressure conditions sufficient to form a two-phase blended composition. The composition comprises: a. 20 to 50 parts by weight-based on a and b total Basis-based crystalline polyolefin selected from homopolymers including polypropylene Acrylic / Ethylene Fine Copolymer, b, 80 to 50 parts by weight-based on the total weight of a and b-an elastic ethylamidine / α-hydrocarbon polymer, the polymer having or not having a polymeric diene in it晞 monomer; c. 1 to 200 parts by weight · • plasticizer for every 100 parts by weight of elastic polymer, the plasticizer is selected from the group consisting of hydrocarbon oils and acid-releasing alkyl esters Wherein the crystalline polyfluorene is at least a co-continuous phase with the ethylene / α-olefin polymer phase. 12. The method according to item 11 of the scope of patent application, wherein the &amp; and b are accepted to be sufficient to form a first melt blend. And the composition's temperature, shear and pressure conditions after the first melt blending composition and c are accepted to form two -3- This paper size applies Chinese National Standard (CNS) A4 specifications (210X 297 mm) 593499 A8 B8 C8 The temperature, shear and pressure conditions of the phase blending composition, the two-phase combination #; the wet COF is greater than the single interaction reaction of the a, b and c composition to accept the temperature, shear and pressure conditions Formed two-phase composition: Wet COF 〇: · 13 · The method according to item 12 of the patent application, wherein the conditions for forming the first and second melt-combination composition and the first melt-blend composition The conditions for forming a two-phase composition are the same. 14. The method according to item 13 of the scope of patent application, wherein the shear, pressure and 0 temperature conditions are provided by a 30 mm twin-screw extruder, which is operated at a screw speed of 400 rpm and the barrel The temperature setting is sufficient to increase the melting temperature of the first blending composition and the two-phase composition to at least 33 ° C (melting temperature + degree of rc.): 15. The method according to any one of items U to 14 of the scope of patent application, wherein ^ The elastomer composition further comprises a material selected from the group consisting of an adhesive, a low molecular weight, low crystallinity polymer, a low molecular weight ethylene / cardiene olefin polymer, and a low molecular weight II propylene copolymer. 16. According to the patent application The composition according to any one of the scope of items from to 2 and is; used to prepare a shaped article having one or more components made from the composition according to any one of the applications of the scope of patent application 1 to 10 The article i has (a) abrasion resistance (ASTM D1630-83, NBS Abrader) which is greater than similar articles made from the same composition but having only a mono-i continuous phase formed from ethylene / α-olefin polymer, and when Existence of components continued, Professional stone bricks; COF measured according to ASTM D-1 894 from 0.3 to 0.07; 17. Shaped articles according to item 16 of the scope of patent application, where coF is 〇 *: to 0.7 〇 · : -4- This paper size applies to China National Standard (CNS) Α4 (210 X 297 mm) 18. · An article of manufacture, which has one or more components based on the composition of any one of claims 1 to 10, the article has abrasion resistance (ASTM D1630_83, NBS Abrader) greater than the system Similar objects from the same composition but with only a single continuous phase formed by the O / W polymer, and when component 0 is present, the COF measured by wet stone bricks according to A / TMD-1894 is used. From 0.3 to 0.7, the article is a plate, film, &gt; king mould molded rubber component, an externally shaped article or a multilayer laminate. 19. · An article of manufacture having one or more components made from a composition according to any one of claims 1 to 10 of the scope of the patent application for the stomach, the article having (a) abrasion resistance (ASTM D1630-83, NBS Abrader ) Is larger than similar articles made from the same composition but having only a single continuous phase formed by the ethylene / α-women polymer, and when component 4 is present, the wet coffee brick measured according to ASTM D-I894 is 0. From 3 to 07, the object is a car body part, a car thermoplastic polywomen part, a car thermoplastic polyolefin vulcanized rubber part, a recreational car part, a gardening device part or an equipment handle. 20 · An article of manufacture having one or more components made from a composition according to any one of items 1 to 10 of the scope of the patent application, the article having (a) abrasion resistance (ASTM m63〇_83, nBS Abrader) is similar to similar articles made from the same composition but having only a single continuous phase formed from an ethylene / α-fluorene polymer, and when component d is present, the COF measured by wet stone bricks according to ASTM D-1894 From 0.3 to 0.7, the object is selected from the outer sole or the bottom of the element, the cushion, the airtight device, the automobile body part, the automobile bumper gauge board, the automobile body side molding, and the automobile exterior decoration , Automotive interior shao decoration, automotive air damping, automotive air ducts, automotive wheel covers and automotive instrument panel skins, trash cans, storage containers, weeders -5- 9 9 4 3 9 5 8 8 8 8 ABC D ^, patent application A group consisting of a range bar, a weeder belt, a utility vehicle part, a water boat part, a roofing film, a boot body, a piping, a door handle, a steering wheel, an armrest, a golf equipment handle, a tennis racket handle, and a squash racket handle. -6- This paper size applies to China National Standard (CNS) A4 (210X 297 mm)