KR20050075748A - Plasticized polyolefin compositions - Google Patents

Abstract

The present invention relates to plasticized polyolefin compositions comprising a polyolefin and a non- functionalized hydrocarbon plasticizer.

Description

Plasticized Polyolefin Composition {PLASTICIZED POLYOLEFIN COMPOSITIONS}

The present invention relates to plasticized polyolefins comprising polyolefins and non-functionalized plasticizers. More specifically, the present invention relates to plasticized polyolefins such as propylene polymers and / or butene polymers with improved properties such as processability, flexibility, ductility and impact resistance.

Polyolefins are useful in many dairy products. However, one disadvantage of many polyolefins, in particular propylene homopolymers and some propylene copolymers, is their relatively high glass transition temperature. Because of this feature, these polyolefins break especially at low temperatures. Polyolefins are advantageous for many applications because of their useful properties over a wide range of temperatures. As a result, there is a need to provide polyolefins that retain or improve their impact strength and toughness at low temperatures while maintaining desirable properties such as high temperature performance or low temperature performance. In particular, it would be advantageous to provide propylene polymers with improved toughness and / or high service temperature without sacrificing other desirable properties.

Adding plasticizers or other materials to polyolefins is one way to improve properties such as impact strength and toughness. Some patent documents relating to this are disclosed in US Patent Nos. 4,960,820, 4,132,698, 3,201,364, WO 02/31044, WO 01/18109 A1 and EP 0 300 689 A2. to be. These documents relate to polyolefins and elastomers mixed with functionalized plasticizers. Functionalized plasticizers are materials such as inorganic oils containing aromatic groups and high (higher than -20 ° C) pour point compounds. The use of these compounds generally does not protect the transparency of polyolefins and often does not improve the impact strength. WO 98/44041 discloses a structure comprising a plastic matrix in a blend comprising a chlorine-free polyolefin or a mixture of polyolefins and a plasticizer, wherein the plasticizer is characterized by an oligomeric polyalphaolefin type material, In particular, a plastic sheet such as a material for flooring is disclosed.

Other background references include EP 0 448 259 A, EP 1 028 145 A, US Pat. Nos. 4,073,782 and 3,415,925.

To the surface of the product, with lower flexural modulus, lower glass transition temperature, and higher impact strength near and below 0 ° C., without substantially affecting the peak melting point, polyolefin crystallization rate, or transparency thereof of the polyolefin. Polyolefins with minimal migration of plasticizers are required. The plasticized polyolefins according to the invention can satisfy this need. More specifically, there is a need for plasticized polypropylene that can be used for use as food containers and toys.

Likewise, plasticized polyolefins with improved ductility, good flexibility (lower bending modulus), reduced glass transition temperature and / or improved impact strength (improved Gardner impact) at low temperatures (below 0 ° C.) The melting point of the polyolefin, the polyolefin crystallization rate or its transparency is not affected and the plasticizer migrates to the product surface produced therefrom to a minimum.

Particular preference is given to plasticizing polyolefins using simple, non-reactive compounds such as paraffin. However, it has been taught that aliphatic or paraffinic compounds impair the properties of polyolefins and are therefore not recommended (see, eg, CHEMICAL ADDITIVES FOR PLASTICS INDUSTRY 107-116 (Radian Corp., Noyes Data Corporation, NJ 1987); Publication No. WO 01/18109 A1).

Inorganic oils which have been used as extenders, softeners and the like in various applications consist of thousands of different compounds, many of which are undesirable in lubrication systems. At normal to elevated temperatures these compounds may oxidize even if they volatilize and add oxidation inhibitors.

Specific inorganic oils, distinguished by viscosity index and the saturated and sulfur content they contain, are listed by the Hydrocarbon Basestock Group I, II or II by the American Petroleum Institute (API). , III). Group I basestocks are solvent purified inorganic oils. It contains the most unsaturated and sulfur and has the lowest viscosity index. This defines the bottom layer of lubricant performance. Group I basestocks are the least expensive to produce and currently account for about 75% of all basestocks. These include most of the "traditional" basestocks. Groups II and III are High Viscosity Index and Very High Viscosity Index basestock. These are hydrotreated inorganic oils. Group III oils contain less unsaturated and sulfur than Group I oils and have a higher viscosity index than Group II oils. Additional basestocks, ie groups IV and V, are also used in the basestock industry. Rudnick and Shubkin describe the five basestock groups as follows:

Group I-Inorganic oils refined using solvent extraction of solvents, solvent dewaxing, hydrogenated tablets to reduce sulfur content, sulfur content of greater than 0.03% by weight, saturate levels of 60-80% and viscosity of about 90 Produces inorganic oils with an index;

Group II-conventional solvent extraction of solvents, solvent dewaxing and more severe hydropurification to reduce the sulfur content below 0.03% by weight, as well as the removal of double bonds from some of the olefinic aromatic compounds, resulting in a saturate amount of 95 to 98 Mildly hydrolyzed inorganic oil, greater than% and having a viscosity index (VI) of about 80 to 120;

Group III-A heavily hydrotreated inorganic oil with a substantially 100% saturation amount of some oils, with a sulfur content of 0.03% or less by weight (preferably 0.001 to 0.01%) and VI greater than 120.

Poly-alpha-olefin-hydrocarbons prepared by catalytic oligomerization of linear olefins having at least carbon atoms of group IV-6. However, in the industrial field, it called a Group IV base stock is "polyalphaolefins," which is generally considered as a class of synthetic basestock fluids produced by oligomerization of alpha olefins of C ₄ or more.

Group V-esters, polyethers, polyalkylene glycols and includes all other basestocks not included in groups I, II, III and IV (see Synthetic Lubricants and High-Performance Functional Fluids , Second edition, Rudnick, Shubkin, eds., Marcel Dekker, Inc. New York, 1999).

Other important references include U.S. Patents 5,869,555, 4,210,570, 4,110,185, British Patents 1,329,915, 3,201,364, 4,774,277, Japanese Patent 01282280, French Patent 2094870, and Japanese Patent 69029554 Rubber Technology Handbook , Werner Hoffman, Hanser Publishers, New York, 1989, pg294-305, Additives for Plastics , J. Stepek, H. Daoust, Springer Verlag, New York, 1983, pg-6-69 have.

U.S. Patent 4,536,537 discloses a mixture of LLDPE (UC 7047), polypropylene 5520 and Synfluid 2CS, 4CS or 6CS with a viscosity of 4.0 to 6.5 cSt at 100 ° F./38° C., while Synfluid 4CS and 8CS It is reported as "not working" (column 3, line 12).

Summary of the Invention

The present invention is directed to plasticized polyolefin compositions comprising at least one polyolefin and at least one non-functionalized plasticizer ("NFP").

The present invention relates to plasticized polyolefin compositions comprising at least one polyolefin and at least one non-functionalized plasticizer ("NFP") having a kinematic viscosity ("KV") at 100 ° C of 2 cSt or less. For the purposes of the present invention, NFP is defined as having a KV of less than 2 cSt at 100 ° C. if it has a flash point of less than 100 ° C.

The present invention also provides plasticization comprising at least one non-functionalized plasticizer which is a polyalphaolefin comprising at least one polyolefin and oligomers of C ₅ to C ₁₄ olefins having a kinematic viscosity of at least 10 cSt and a viscosity index of at least 120 at 100 ° C. To a polyolefin composition.

The invention also relates to a plasticized polypropylene composition comprising polypropylene and at least one non-functionalized plasticizer comprising an oligomer of C ₅ to C ₁₄ olefins having a viscosity index of at least 120, provided that the plasticization The composition comprises 4 to 10% by weight of polyalphaolefin, a hydrogenated and highly branched dimer of an alpha olefin having 8 to 12 carbon atoms, the composition being 18 to 25% by weight linear low density polyethylene having a density of 0.912 to 0.935 g / cc. Does not contain%

The invention also relates to a plasticized polypropylene composition comprising polypropylene and at least one non-functionalized plasticizer comprising an oligomer of C ₆ to C ₁₄ olefins having a viscosity index of at least 120, provided that the composition is It does not include impact copolymers of polypropylene and 40-50% by weight of ethylene propylene rubber or the composition does not include random copolymers of propylene and ethylene.

The invention also includes one or more non-functionalized plasticizers comprising one or more polyolefins and linear and / or branched paraffinic hydrocarbon compositions produced by one or more gas to liquid processes having a number average molecular weight of 500 to 20,000. It relates to a plasticized polyolefin composition.

FIG. 1 is a graph showing Storage Modulus (E ′) as a function of temperature for various plasticized propylene homopolymer examples cited herein.

2 is a graph showing Tan δ as a function of temperature for various plasticized propylene homopolymer examples cited herein.

3 is a graph showing Tan δ as a function of temperature for various plasticized propylene copolymer examples cited herein.

4 is a graph showing Tan δ as a function of temperature for various plasticized propylene impact copolymer examples cited herein.

5 is a graph showing melt heat flow from DSC as a function of temperature for various plasticized propylene homopolymer samples illustrating the present invention.

6 is a graph showing crystallization heat flow from DSC as a function of temperature for various plasticized propylene homopolymer samples illustrating the present invention.

FIG. 7 is a graph showing melt heat flow from DSC as a function of temperature for various plasticized propylene copolymer samples illustrating the present invention.

FIG. 8 is a graph showing the crystallization heat flow from DSC as a function of temperature for various plasticized propylene copolymer samples illustrating the present invention.

9 is a graph showing melt heat flow from DSC as a function of temperature for various plasticized propylene impact copolymer samples illustrating the present invention.

10 is a graph showing the crystallization heat flow from DSC as a function of temperature for various plasticized propylene impact copolymer samples illustrating the present invention.

11 is a graph showing shear viscosity as a function of shear rate for various plasticized propylene homopolymer samples illustrating the present invention.

12 is a graph showing shear viscosity as a function of shear rate for various plasticized propylene copolymer samples illustrating the present invention.

13 is a graph showing shear viscosity as a function of shear rate for various plasticized propylene impact copolymer samples illustrating the present invention.

14 is a graph showing molecular weight distribution for various plasticized propylene homopolymer samples illustrating the present invention.

Justice

For the purposes of the present invention and the claims appended hereto, polymers or oligomers include olefins, wherein the olefins present in the polymer or oligomer are each a polymerized or oligomerized form of the olefin. Likewise, the term polymer is used to mean both homopolymers and copolymers. The term copolymer also includes any polymer having two or more monomers. Thus, as used herein, "polypropylene" means at least 50%, preferably at least 70%, more preferably at least 80%, more preferably at least 90%, even more preferably at least 95%, or propylene units, or It means a polymer consisting of 100%.

For the purposes of the present invention, oligomers are less than 21,000 g / mol, preferably less than 20,000 g / mol, preferably less than 19,000 g / mol, preferably less than 18,000 g / mol, preferably less than 16,000 g / mol , Preferably with less than 15,000 g / mol, preferably less than 13,000 g / mol, preferably less than 10,000 g / mol, preferably less than 5000 g / mol, preferably less than 3000 g / mol Is defined.

For the purposes of the present invention and the claims appended hereto, groups I, II and III basestocks are defined as being inorganic oils having the following properties.

The present invention is directed to plasticized polyolefin compositions comprising at least one polyolefin and at least one non-functionalized plasticizer ("NFP").

Generally, the polyolefin is 40 to 99.9 weight percent (based on the weight of the polyolefin and NFP) in the composition of the present invention in one embodiment, 50 to 99 weight percent in another embodiment, 60 to 60 weight in another embodiment 98 wt%, in another embodiment 70-97 wt%, in another embodiment 80-97 wt%, in another embodiment 90-98 wt%, with preferred ranges described herein It can be any combination of any weight percent upper limit and any weight percent limit.

In another embodiment of the invention, the plasticized polyolefin is 50 to 99.99% by weight, optionally 60 to 99% by weight, optionally 70 to 98% by weight, optionally 80 to 97, based on the weight of the polypropylene and NFP Weight percent, optionally 90 to 96 weight percent polypropylene, wherein the NFP is 50 to 0.01 weight percent, alternatively 40 to 1 weight percent, alternatively 30 to 2 weight percent, alternatively 20 to 3 weight percent, Alternatively 10 to 4% by weight.

In another embodiment, the plasticized polyolefin comprises 50 to 99.99 weight percent, optionally 60 to 99 weight percent, alternatively 70 to 98 weight percent, alternatively 80 to 97 weight percent, based on the weight of the polybutene and NFP, Alternatively 90 to 96% by weight of polybutene, wherein the NFP is 50 to 0.01% by weight, alternatively 40 to 1% by weight, optionally 30 to 2% by weight, optionally 20 to 3% by weight, optionally It is present in an amount of 10 to 4% by weight.

In another embodiment, the polyolefin comprises polypropylene and / or polybutene, and the NFP is 0.01 to 50% by weight, more preferably 0.05 to 45% by weight, more preferably based on the weight of the polypropylene and NFP. 0.5 to 40% by weight, more preferably 1 to 35% by weight, more preferably 2 to 30% by weight, more preferably 3 to 25% by weight, more preferably 4 to 20% by weight, more preferably It is present in 5 to 15% by weight. In another embodiment, the NFP is present at 1-15% by weight, preferably 1-10% by weight, based on the weight of the polypropylene and / or polybutene and NFP.

In another embodiment of the present invention, the NFP is present at 3% by weight or more based on the weight of the polyolefin and the NFP.

For the purposes of the present invention and the claims appended hereto, the amount of NFP in a given composition is determined by the extraction technique described below as Method 1: Extraction . The CRYSTAF method is also described for comparison purposes.

For the purposes of the present invention and the claims appended hereto, when the melting point is mentioned and there is a melting point range, the melting point is defined as being the peak melting point from the DSC trace as described below.

Non-functionalized plasticizer

The polyolefin composition of the present invention comprises a non-functionalized plasticizer ("NFP"). NFPs of the present invention are compounds comprising carbon and hydrogen and functional groups selected from the group consisting of hydroxides, aryls and substituted aryls, halogens, alkoxy, carboxylates, esters, carbon unsaturateds, acrylates, oxygen, nitrogen and carboxyl Does not include enough. “A significant amount” means, in one embodiment, less than 5 weight percent, more preferably less than 4 weight percent, more preferably, based on the weight of the NFP, in one embodiment even if these functional groups and compounds comprising them are present without deliberate addition to the NFP. Preferably less than 3%, more preferably less than 2%, more preferably less than 1%, more preferably less than 0.7%, more preferably less than 0.5%, more preferably 0.3% Less than, more preferably less than 0.1%, more preferably less than 0.05%, more preferably less than 0.01%, more preferably less than 0.001% by weight.

In one embodiment, the NFP comprises C ₆ to C ₂₀₀ paraffins, and in another embodiment C ₈ to C ₁₀₀ paraffins. In another embodiment, the NFP consists essentially of C ₆ to C ₂₀₀ paraffins, and in another embodiment consists of C ₈ to C ₁₀₀ paraffins. For the purposes of the present invention and the description herein, "paraffin" includes all isomers such as n-paraffins, branched paraffins, isoparaffins and may include cyclic aliphatic species and mixtures thereof, The crude oil may be derived synthetically by known means or derived from refined crude oil in a manner that meets the requirements described for the preferred NFP described herein. It will be appreciated that the class of materials described herein useful as NFPs may be used alone or in combination with other NFPs described herein to achieve the desired properties.

The invention also relates to at least one polyolefin and to kinematic viscosity (“KV”) of 2 cSt or less at 100 ° C., preferably 1.5 cSt or less, preferably 1.0 cSt or less, preferably 0.5 cSt or less (measured by ASTM D445). A plasticized polyolefin composition comprising at least one nonfunctionalized plasticizer having kinematic viscosity. In one other embodiment, NFP having a KV of less than 2 cSt at 100 ° C. may also have a glass transition temperature (Tg) which may not be measured by ASTM E 1356 or may be measured, but Tg according to ASTM E 1356 is less than 30 ° C. , Preferably less than 20 ° C, more preferably less than 10 ° C, more preferably less than 0 ° C, more preferably less than -5 ° C, even more preferably less than -10 ° C, more preferably less than -15 ° C. to be.

In another embodiment, it has a KV of less than or equal to 2 cSt at 100 ° C., and optionally has a glass transition temperature (Tg), which may not be measured by ASTM E 1356, or may be less than 30 ° C., preferably 20 ° C. NFPs having a Tg according to ASTM E 1356 of less than, more preferably less than 10 ° C, more preferably less than 0 ° C, more preferably less than -5 ° C, have one or more of the following properties:

1.40 ° C. or less, preferably 35 ° C. or less, preferably 30 ° C. or less, preferably 25 ° C. or less, preferably 20 ° C. or less, preferably 15 ° C. or less, preferably 10 ° C. or less, preferably Is a distillation range measured by ASTM D 86 having a difference between an upper temperature and a lower temperature of 6 to 40 ° C., preferably 6 to 30 ° C .; And / or

2. Greater than 100 ° C, preferably greater than 110 ° C, preferably greater than 120 ° C, preferably greater than 130 ° C, preferably greater than 140 ° C, preferably greater than 150 ° C, preferably Greater than 160 ° C, preferably greater than 170 ° C, preferably greater than 180 ° C, preferably greater than 190 ° C, preferably greater than 200 ° C, preferably greater than 210 ° C, preferably 220 ° C An initial boiling point measured by ASTM D 86 that is greater than, preferably greater than 230 ° C., preferably greater than 240 ° C .; And / or

3. 10 ° C or less, preferably 0 ° C or less, preferably -5 ° C or less, preferably -15 ° C or less, preferably -40 ° C or less, preferably -50 ° C or less, preferably -60 Pour point below C (measured by ASTM D 97); And / or

4. Less than 0.88, preferably less than 0.85, preferably less than 0.80, preferably less than 0.75, preferably less than 0.70, preferably 0.65 to 0.88, preferably 0.70 to 0.86, preferably 0.75 to 0.85, Preferably specific gravity of 0.79 to 0.85, preferably 0.800 to 0.840 (ASTM D 4052, 15.6 / 15.6 ° C.); And / or

5. Final boiling point measured by ASTM D 86 of 115 to 500 ° C., preferably 200 to 450 ° C., preferably 250 to 400 ° C .; And / or

6. weight average molecular weight (Mw) of 2,000 to 100 g / mol, preferably 1500 to 150, preferably 1000 to 200; And / or

7. Number average molecular weight (Mn) of 2,000 to 100 g / mol, preferably 1500 to 150, preferably 1000 to 200; And / or

8. Flash point measured by ASTM D 56 between -30 and 150 ° C; And / or

9. Dielectric constant at 20 ° C. of less than 3.0, preferably less than 2.8, preferably less than 2.5, preferably less than 2.3, preferably less than 2.1; And / or

10. Density of 0.70 to 0.83 g / cm 3 (ASTM 4052, 15.6 / 15.6 ° C.); And / or

11.viscosity of 0.5-20 cSt at 25 ° C. (ASTM 445, 25 ° C.); And / or

12. 6 to 150 carbon atoms, preferably 7 to 100, preferably 10 to 30, preferably 12 to 25.

In certain embodiments of the invention, the NFP having a KV of 2 cSt or less at 100 ° C. is preferably C ₆ to C ₁₅₀ isoparaffin, preferably C ₆ to C ₁₀₀ isoparaffin, preferably C ₆ to C ₂₅ 50% by weight, preferably 60% by weight, preferably 70% by weight, preferably 80% by weight, preferably 90% by weight of isoparaffin, more preferably C ₈ to C ₂₀ isoparaffin Or more, preferably 95% by weight or more, preferably 100% by weight. Isoparaffin means that the paraffin chain has a C ₁ to C ₁₀ alkyl branch along at least a portion of each paraffin chain. More specifically, isoparaffins are saturated aliphatic hydrocarbons having one or more carbon atoms bonded to at least three other carbon atoms or at least one side chain (ie, molecules having one or more tertiary or quaternary carbon atoms). Preferably, the total number of carbon atoms per molecule is from 6 to 50, in another embodiment from 10 to 24, in another embodiment from 10 to 15. Various isomers of each carbon number will typically be present. Isoparaffins also generally include cycloparaffins having branched side chains as a minor component of isoparaffins. Preferably the density of these isoparaffins (ASTM 4052, 15.6 / 15.6 ° C.) is 0.70 to 0.83 g / cm 3, the pour point is -40 ° C. or less, preferably -50 ° C. or less, and the viscosity (ASTM 445, 25 ° C.) Is 0.5 to 20 cSt at 25 ° C. and an average molecular weight is 100 to 300 g / mol. Suitable isoparaffins are sold under the trade name ISOPAR [ExxonMobil Chemical Company, Houston, Texas, USA] and are disclosed in U.S. Pat.Nos. 6,197,285, 3,818,105 and 3,439,088 and as the ISOPAR series of isoparaffins. Commercially available, some of which are summarized in Table 1.

In one embodiment, isoparaffin is a mixture of branched paraffins and normal paraffins having 6 to 50 carbon atoms in the molecule, and in another embodiment 10 to 24 carbon atoms. Isoparaffin compositions have a branched paraffin to n-paraffins ratio (branched paraffin: n-paraffins) of 0.5: 1 to 9: 1 in one embodiment and 1: 1 to 4: 1 in another embodiment. In this embodiment the isoparaffins of the mixture comprise at least 50% by weight (based on the total weight of the isoparaffin composition) of mono-methyl species, such as 2-methyl, 3-methyl, 4-methyl, 5-methyl, and the like. The formation of branches containing, and having more than 1 carbon substituents such as ethyl, propyl, butyl, etc., forms minimally based on the total weight of isoparaffins in the mixture. In one embodiment, the isoparaffins in the mixture contain at least 70% by weight mono-methyl species, based on the total weight of the isoparaffins in the mixture. The isoparaffinic mixture is boiled in one embodiment at 100-350 ° C., in another embodiment in the range of 110-320 ° C. When producing different grades, the paraffinic mixture is generally fractionated into sections having a narrow boiling range, for example a 35 ° C. boiling range. These branched paraffin / n-paraffin blends are disclosed in US Pat. No. 5,906,727.

Other suitable isoparaffins are also sold under the trade names SHELLSOL (Shell), SOLTROL (Chevron Phillips) and SASOL (Sasol Limited). SHELLSOL is a product of the Royal Dutch / Shell Group of Companies, for example Shellsol ™ (boiling point = 215-260 ° C.). SOLTROL is a product of Chevron Phillips Chemical Company Limited, for example SOLTROL 220 (boiling point = 233 to 280 ° C). SASOL is a product of Sasol Limited, Johannesburg, South Africa, for example SASOL LPA-210, SASOL-47 (boiling point = 238 to 274 ° C).

In certain embodiments of the invention, NFPs having a KV of 2 cSt or less at 100 ° C. are preferably C ₅ to C ₂₅ n-paraffins, preferably C having an aromatics of less than 0.1%, preferably less than 0.01% ₅ to C ₂₀ n-paraffins, preferably C ₅ to C ₁₅ n-paraffins at least 50% by weight, preferably at least 60% by weight, preferably at least 70% by weight, preferably at least 80% by weight, preferably Preferably at least 90% by weight, preferably at least 95% by weight, preferably 100% by weight. In a preferred embodiment, the n-paraffins have a distillation range of 30 ° C. or lower, 20 ° C. or lower, and / or an initial boiling point of 150 ° C. or higher, preferably 200 ° C. or higher, and / or 0.65 to 0.85, preferably 0.70 to 0.80, preferably Preferably with a specific gravity of 0.75 to 0.80 and / or a flash point greater than 60 ° C, preferably greater than 90 ° C, preferably greater than 100 ° C, preferably greater than 120 ° C.

Suitable n-paraffins are sold under the trade name NORPAR (ExxonMobil Chemical Company, Houston, TX) and are marketed as the NORPAR series of n-paraffins, some of which are summarized in Table 1a below.

In certain embodiments of the invention, the NFP having a KV of 2 cSt or less at 100 ° C. is preferably at least 50% by weight, preferably at least 50% by weight, of dearomatized aliphatic hydrocarbons comprising a mixture of normal paraffins, isoparaffins and cycloparaffins. At least 60% by weight, preferably at least 70% by weight, preferably at least 80% by weight, preferably at least 90% by weight, preferably at least 95% by weight, preferably 100% by weight. Generally they are a mixture of C ₄ to C ₂₅ , preferably C ₅ to C ₁₈ , preferably C ₅ to C ₁₂ normal paraffins, isoparaffins and cycloparaffins. They contain very low amounts of aromatic hydrocarbons, preferably less than 0.1, preferably less than 0.01. In a preferred embodiment, the dearomatized aliphatic hydrocarbon has a distillation range of 30 ° C. or lower, 20 ° C. or lower, and / or an initial boiling point greater than 110 ° C., preferably greater than 200 ° C., and / or 0.65 to 0.85, preferably 0.70. To 0.85, preferably 0.75 to 0.85, preferably 0.80 to 0.85 (15.6 / 15.6 ° C.), and / or greater than 60 ° C., preferably greater than 90 ° C., preferably greater than 100 ° C., preferred Preferably having a flash point greater than 110 ° C.

Suitable dearomatized aliphatic hydrocarbons are sold under the tradename EXXSOL (ExxonMobil Chemical Company, Houston, TX) and are marketed as the EXXSOL series of dearomatized aliphatic hydrocarbons, summarized in Table 1b below.

The invention also relates to C ₆ to C ₁₄ olefins having at least one polyolefin, preferably polypropylene or polybutene, more preferably polypropylene, and a kinematic viscosity of at least 10 cSt at 100 ° C. and a viscosity index of at least 120, preferably at least 130 A plasticized polyolefin composition comprising at least one nonfunctionalized plasticizer comprising a polyalphaolefin comprising an oligomer of.

The invention also relates to a plasticized polypropylene composition comprising polypropylene and at least one non-functionalized plasticizer comprising an oligomer of C ₆ to C ₁₄ olefins having a viscosity index of at least 120, provided that the plasticization The composition comprises 4 to 10% by weight of polyalphaolefin, a hydrogenated and highly branched dimer of an alpha olefin having 8 to 12 carbon atoms, the composition being 18 to 25% by weight linear low density polyethylene having a density of 0.912 to 0.935 g / cc. Does not contain%

The invention also relates to a plasticized polypropylene composition comprising polypropylene and at least one non-functionalized plasticizer comprising an oligomer of C ₆ to C ₁₄ olefins having a viscosity index of at least 120, provided that the polyolefin comprises It does not include impact copolymers of polypropylene and 40-50% by weight of ethylene propylene rubber or the composition does not include random copolymers of propylene and ethylene.

In another embodiment, the NFP has a kinematic viscosity of at least 10 (measured by ASTM D 445), and preferably at least 100, preferably at least 110, more preferably at least 120, more as measured by ASTM D-2270. Preferably a viscosity index ("VI") of at least 130, more preferably at least 140, and / or a pour point of less than -5 ° C, more preferably at most -10 ° C, more preferably at most -20 ° C (ASTM D). Polyalphaolefins comprising oligomers of linear olefins having from 6 to 14, more preferably from 8 to 12, more preferably from 10.

In another embodiment, polyalphaolefin oligomers useful in the present invention are C ₂₀ to C ₁₅₀₀ paraffins, preferably C ₄₀ to C ₁₀₀₀ paraffins, preferably C ₅₀ to C ₇₅₀ paraffins, preferably C ₅₀ to C ₅₀₀ Paraffin. PAO oligomers in one embodiment are C ₅ to C ₁₄ alpha-olefins, in another embodiment C ₆ to C ₁₂ alpha-olefins, in another embodiment dimers, trimers, of C ₈ to C ₁₂ alpha-olefins, Tetramers, pentamers, and the like. Suitable olefins include 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene and 1-dodecene. In one embodiment, the olefin is 1-decene and the NFP is a mixture of dimers, trimers, tetramers, and pentamers (and more) of 1-decene. Preferred PAOs are more specifically described, for example, in U.S. Pat. 1999].

PAOs useful in the present invention generally have a number average molecular weight of 100 to 21,000 in one embodiment, 200 to 10,000 in another embodiment, 200 to 7,000 in another embodiment, 200 to 2,000 in another embodiment, and another embodiment. It has a number average molecular weight of 200 to 500 in the sun. Preferred PAOs have a viscosity of from 0.1 to 150 cSt at 100 ° C., and from 0.1 to 3000 cSt (ASTM 445) in another embodiment. PAOs useful in the present invention generally have a pour point of less than 0 ° C. in one embodiment, less than −10 ° C. in another embodiment, less than −20 ° C. in another embodiment, and less than −40 ° C. in another embodiment. Preferred PAOs are commercially available as SHF and SuperSyn PAO (ExxonMobil Chemical Company, Houston, TX), and some are summarized in Table 2 below.

Other useful PAOs are Synfluid® from Chevron Phillips Chemical Company, Pasadena, Texas, USA, Durasyn® from BP Amoco Chemicals, London, UK, Finland Nexbase (R), marketed by Fortum Oil and Gas, Synton (R), marketed by Crompton Corporation, Middlebury, Connecticut, Cornis Corporation, Ohio, USA EMERY® sold by Cognis Corporation.

In one embodiment, the PAO has a kinematic viscosity of at least 10 cSt at 100 ° C., preferably at least 30 cSt, preferably at least 50 cSt, preferably at least 80 cSt, preferably at least 110 cSt, preferably at least 150 cSt, preferably at least 200 cSt, It preferably has a kinematic viscosity of at least 500 cSt, preferably at least 750 cSt, preferably at least 1000 cSt, preferably at least 1500 cSt, preferably at least 2000 cSt, preferably at least 2500 cSt. In another embodiment, the PAO has a kinematic viscosity at 100 ° C. of 10 to 3000 cSt, preferably 10 to 1000 cSt, preferably 10 to 40 cSt.

In another embodiment, the PAO is at least 120, preferably at least 130, preferably at least 140, preferably at least 150, preferably at least 170, preferably at least 190, preferably at least 200, preferably It has a viscosity index of 250 or more, preferably 300 or more.

In a particularly preferred embodiment, the PAO has a kinematic viscosity of at least 10 cSt at 100 ° C. when the polypropylene is RB 501 F, Hilfax CA12A, or ADFLEX Q 100F as disclosed in WO 98/44041.

The invention also relates to one or more polyolefins and to 6 to 1500, preferably 8 to 1000, preferably 10 to 500, preferably 12 to 200, preferably 14 to 150, preferably 16 to 100 carbon atoms in the molecule. A plasticized polyolefin composition comprising at least one non-functionalized plasticizer comprising a high purity hydrocarbon fluid composition comprising a mixture of paraffins. The hydrocarbon fluid composition has an isoparaffin: n-paraffin ratio of about 0.5: 1 to about 9: 1, preferably about 1: 1 to about 4: 1. The isoparaffins of the mixture contain more than 50% of mono-methyl species, such as 2-methyl, 3-methyl, 4-methyl, 5-methyl, and more than 1 carbon substituents such as ethyl, Branches with propyl, butyl and the like form at least based on the total weight of isoparaffins in the mixture. Preferably, the isoparaffins of the mixture contain at least 70% by weight of mono-methyl species based on the total weight of isoparaffins in the mixture. These hydrocarbon fluids preferably have a viscosity KV of 1 to 100,000 cSt, preferably 10 to 2000 cSt at 25 ° C., optionally up to −20 ° C., more preferably up to −30 ° C., more preferably about −20 To a low pour point of from about -70 ° C. These hydrocarbon fluids preferably have a viscosity KV of from 1 to 30,000 cSt, preferably from 10 to 2000 cSt, at 40 ° C., optionally at most −20 ° C., more preferably at most −30 ° C., more preferably about − It has a low pour point of 20 to about -70 ℃.

The invention also relates to plasticized polyolefin compositions comprising at least one polyolefin and at least one non-functionalized plasticizer comprising a linear or branched paraffinic hydrocarbon composition having the following properties:

1. a number average molecular weight of 500 to 21,000 g / mol;

2. less than 10%, preferably less than 8%, preferably less than 5%, preferably less than 3%, preferably less than 2%, preferably less than 1% by weight, of 4 or more side chains, Preferably less than 0.5% by weight, preferably less than 0.1% by weight, preferably less than 0.01% by weight, preferably less than 0.001% by weight;

3. at least 15% by weight, preferably at least 20% by weight, preferably at least 25% by weight, preferably at least 30% by weight, preferably at least 35% by weight, preferably at least 40% by weight, preferably At least one or two carbon branches present at least 45% by weight, preferably at least 50% by weight;

4. less than 2.5% by weight of cyclic paraffins, preferably less than 2% by weight, preferably less than 1% by weight, preferably less than 0.5% by weight, preferably less than 0.1% by weight, preferably less than 0.01% by weight, Preferably less than 0.001% by weight. In another embodiment, these NFPs have a kinematic viscosity of at least 2 cSt at 100 ° C. and / or at least 120, preferably at least 130, preferably at least 140, preferably at least 150, preferably at least 170, preferably at least 190 , Preferably at least 200, preferably at least 250, preferably at least 300.

In another embodiment, the NFP comprises a high purity hydrocarbon fluid composition comprising a mixture of paraffins having a carbon number of about C ₈ to C ₂₀ and a molar ratio of isoparaffins: n-paraffins from about 0.5: 1 to about 9: 1 Wherein the isoparaffin of the mixture contains more than 50% mono-methyl species based on the total weight of the isoparaffin of the mixture, and the composition has a pour point of about -20 to about -70 ° F and about 1 to about at 25 ° C. It has a kinematic viscosity of 10 cSt.

In another embodiment, the mixture of paraffins has from about C ₁₀ to about C ₁₆ carbon atoms. In another embodiment, the mixture contains more than 70% mono-methyl species. In another embodiment, the mixture boils at a temperature ranging from about 320 to about 650 ° F. In another embodiment, the mixture boils in a temperature range of about 350 to about 550 ° F. In another embodiment, the mixture comprises a paraffin mixture of carbon atoms of about C ₁₀ to about C ₁₆ . In another embodiment, the mixture has about C ₁₀ to C ₁₆ carbon atoms and the mixture contains more than 70% mono-methyl species and boils in a temperature range of about 350 to about 550 ° F. In another embodiment, the mixture has a molar ratio of isoparaffin: n-paraffins from about 1: 1 to about 4: 1. In another embodiment, the mixture is derived from a Fischer-Tropsch process. Such NFP may be prepared by the method disclosed in US Pat. No. 5,906,727.

Any NFP may also be described by any number or any combination of factors described herein. In one embodiment, any NFP of the present invention is less than 0 ° C in one embodiment, less than -5 ° C in another embodiment, less than -10 ° C in another embodiment, and less than -20 ° C in another embodiment. , In another embodiment, below -40 ° C, in another embodiment, below -50 ° C, in another embodiment, below -60 ° C, in another embodiment, above -120 ° C, in another embodiment, above -200 ° C. With a pour point (ASTM D97), preferred ranges may include any of the lower pour point and any upper pour point disclosed herein. In one embodiment, the NFP is a paraffin or other compound having a pour point below −30 ° C., in another embodiment from −30 ° C. to −90 ° C., and a viscosity range from 40 ° C. to 0.5 to 200 cSt (ASTM D445-97). In general, most inorganic oils comprising aromatic moieties and other functional groups have a pour point of 10 to -20 ° C in the same viscosity range.

In another embodiment, the NFP described herein is at least 90, preferably at least 95, more preferably at least 100, more preferably at least 105, more preferably at least 110, more preferably at least 115, more Preferably it has a viscosity index of 120 or more, more preferably 125 or more, more preferably 130 or more. In another embodiment, the NFP has a VI of 90 to 400, preferably 120 to 350.

Any of the NFPs described herein is at 20 ° C. of less than 3.0 in one embodiment, less than 2.8 in another embodiment, less than 2.5 in another embodiment, less than 2.3 in another embodiment, and less than 2.1 in another embodiment. It can have a dielectric constant. Polyethylene and polypropylene each have a dielectric constant of at least 2.3 (1 kHz, 23 ° C.) (CRC HANDBOOK OF CHEMISTRY AND PHYSICS (David R. Lide, ed. 82 ^d ed. CRC Press 2001)).

In some embodiments, the NFP is 0.1 to 3000 cSt at 100 ° C., 0.5 to 1000 cSt at 100 ° C. in another embodiment, 1 to 250 cSt at 100 ° C. in another embodiment, 1 to 200 cSt at 100 ° C. in another embodiment, In another embodiment it may have a kinematic viscosity (ASTM D445-97) of 10 to 500 cSt at 100 ° C., and preferred ranges may include any of the upper and lower viscosity limits described herein. In another embodiment, the NFP has a kinematic viscosity of less than 2 cSt at 100 ° C.

In some embodiments, the NFP described herein is less than 0.920 in one embodiment, less than 0.910 in another embodiment, 0.650 to 0.900 in another embodiment, 0.700 to 0.860 in another embodiment, 0.750 in another embodiment. To 0.855, in another embodiment 0.790 to 0.850, and in still another embodiment, specific gravity (ASTM D 4052, 15.6 / 15.6 ° C.), with preferred ranges including any specific upper and lower specific gravity values described herein. can do.

In another embodiment, any NFP described herein has a boiling point of 100 to 500 ° C. in one embodiment, 200 to 450 ° C. in another embodiment and 250 to 400 ° C. in another embodiment. In addition, the NFP is preferably less than 20,000 g / mol in one embodiment, less than 10,000 g / mol in another embodiment, less than 5,000 g / mol in another embodiment, less than 4,000 g / mol in another embodiment, Having a weight average molecular weight of less than 2,000 g / mol in another embodiment, less than 500 g / mol in another embodiment and less than 100 g / mol in another embodiment, the preferred molecular weight range being any upper molecular weight limit described herein. And any arbitrary lower limit of molecular weight.

In another embodiment, the NFP comprises a Group III hydrocarbon basestock. Preferably the NFP is at least 90%, preferably at least 92%, preferably at least 94%, preferably at least 96%, preferably at least 98%, preferably at least 99% saturate level, and 0.03% Inorganic oils having a sulfur content of less than, preferably 0.001 to 0.01%, VI is at least 120, preferably at least 130.

In some embodiments, polybutene is useful as the NFP of the present invention. In one embodiment of the invention, the polybutene process oil has a low molecular weight (number average molecular weight of less than 15,000; weight less than 60,000) of olefin derived units having 3 to 8 carbon atoms in one embodiment and 4 to 6 carbon atoms in another embodiment. Average molecular weight) homopolymer or copolymer. In another embodiment, the polybutene is a homopolymer or copolymer of C ₄ raffinate. Embodiments of low molecular weight polymers called such "polybutene" polymers are described, for example, in SYNTHETIC LUBRICANTS AND HIGH-PERFORMANCE FUNCTIONAL FLUIDS 357-392 (Leslie R. Rudnick & Ronald L. Shubkin, ed., Marcel Dekker 1999). (Hereinafter referred to as "polybutene processing oil" or "polybutene"). Another preferred embodiment includes poly (n-butene) hydrocarbons. Preferred poly (n-butenes) have a number average molecular weight of less than 15,000 and a weight average molecular weight of less than 60,000.

In another preferred embodiment, the polybutene is a copolymer of at least isobutylene derived units, 1-butene derived units and 2-butene derived units. In one embodiment, the polybutene is a homopolymer, copolymer, or three unit terpolymer, wherein the isobutylene derived units comprise 40-100% by weight of the copolymer and the 1-butene derived units 0-40% by weight of the copolymer and 2-butene derived units are 0-40% by weight of the copolymer. In another embodiment, the polybutene is a copolymer or terpolymer of three units, wherein the isobutylene derived units are 40-99% by weight of the copolymer and the 1-butene derived units are 2 To 40% by weight and 2-butene derived units are 0 to 30% by weight of the copolymer. In another embodiment, the polybutene is a terpolymer of three units, wherein the isobutylene derived units are 40-96 wt% of the copolymer and the 1-butene derived units are 2-40 wt% of the copolymer %, And the 2-butene derived unit is 2 to 20% by weight of the copolymer. In another embodiment, the polybutene is a homopolymer or copolymer of isobutylene and 1-butene, wherein the isobutylene derived units are 65 to 100% by weight of the homopolymer or copolymer and 1-butene derived The unit is 0 to 35% by weight of the copolymer.

Polybutene process oils useful in the present invention generally have a number average molecular weight (Mn) of less than 10,000 g / mol in one embodiment, less than 8000 g / mol in another embodiment and less than 6,000 g / mol in another embodiment. . In one embodiment, the polybutene oil has a number average molecular weight greater than 400 g / mol, in another embodiment greater than 700 g / mol, and in another embodiment greater than 900 g / mol. Preferred embodiments may be a combination of any of the upper and lower molecular weight limits described herein. For example, in one embodiment of the polybutene of the present invention, the polybutene has a number of 400 to 10,000 g / mol, in another embodiment 700 to 8,000 g / mol, and in another embodiment a number of 900 to 3,000 g / mol It has an average molecular weight. Useful viscosities of the polybutene processing oil are in one embodiment 10 to 6000 cSt (centistoke) at 100 ° C., in another embodiment 35 to 5000 cSt at 100 ° C. and in another embodiment greater than 35 cSt at 100 ° C., and in another embodiment In an embodiment greater than 100 cSt at 100 ° C.

Commercial examples of useful polybutenes include the PARAPOL® series of process oils (Infineum, Linden, NJ), for example PARAPOL® 450, 700, 950, 1300, 2400 and 2500 and poly Butene's Infinium “C” series, for example C9945, C9900, C9907, C9913, C9922, C9925, as listed below. The commercially available PARAPOL® and Infinium series of polybutene processed oils are synthetic liquid polybutenes, each blend having a specific molecular weight and all blends can be used in the compositions of the present invention. The molecular weight of PARAPOL® oil is from 420 Mn (PARAPOL® 450) to 2700 Mn (PARAPOL® 2500) as measured by gel permeation chromatography. The MWD of PARAPOL® oil is 1.8 to 3 in one embodiment and 2 to 2.8 in another embodiment; The pour point of these polybutenes is less than 25 ° C in one embodiment, less than 0 ° C in another embodiment, less than -10 ° C in another embodiment, -80-25 ° C in another embodiment, and a density (at 20 ° C). IP 190/86) is from 0.79 to 0.92 g / cm 3, in another embodiment from 0.81 to 0.90 g / cm 3.

Tables 3 and 3a below show the properties of PARAPOL® oils and infinium oils useful in embodiments of the invention, wherein the viscosity is measured according to ASTM D445-97, and the number average molecular weight (Mn) is gel permeable. Measured by chromatography.

Thus, preferred NFPs for use in the present invention may be described by any of the embodiments described herein or any combination of the embodiments disclosed herein. For example, in one embodiment, the NFP is C ₆ to C ₂₀₀ paraffin with a pour point of less than -25 ° C. Stated another way, the NFP includes aliphatic hydrocarbons having a viscosity of 0.1 to 1000 cSt at 100 ° C. Stated another way, the NFP is selected from n-paraffins having 8 to 25 carbon atoms, branched isoparaffins and mixtures thereof.

Preferred NFPs of the present invention, when mixed with polyolefins to form plasticizing compositions, have no change in the number of peaks in the DMTA traces as compared to the unplasticized polyolefin Dynamic Mechanical Thermal Analysis (DMTA) traces. In view of the above, NFP can be mixed with polyolefin. Lack of miscibility can be seen by the increased number of peaks in DMTA traces than in unplasticized polyolefins. This trace is a schematic of Tan δ temperature as described below.

Preferred compositions of the invention are in one embodiment at least 2 ° C. for every 4% by weight NFP present in the composition, in another embodiment at least 3 ° C. for every 4% by weight NFP, in another embodiment While the glass transition temperature (Tg) of the composition decreases by 4 to 10 ° C. for every 4% by weight of NFP, the peak melting point and crystallization temperature of the polyolefin are maintained constant (within 1 to 2 ° C.). For the purposes of the present invention and the claims appended hereto, glass transition temperature refers to the peak temperature in the DMTA trace.

Preferred compositions of the present invention are, in one embodiment, at least 2 ° C, preferably at least 3 ° C, preferably at least 4 ° C, preferably at least 5 ° C, relative to every 1% by weight of NFP of the NFP present in the composition. By at least 6 ° C., preferably by at least 7 ° C., preferably by at least 8 ° C., preferably by at least 9 ° C., preferably by at least 10 ° C., and preferably by at least 11 ° C. As the glass transition temperature (Tg) of the composition decreases, the peak melting point and crystallization temperature of the pure polyolefin is within 1 to 5 ° C., preferably within 1 to 4 ° C., preferably within 1 to 3 ° C. of the plasticized polyolefin, Preferably it is characterized in that it is maintained within 1 to 2 ℃.

Preferred compositions of the present invention have a glass transition temperature (Tg) of the plasticized composition of 2 ° C or higher, preferably 4 ° C or higher, preferably 6 ° C or higher, preferably 8 ° C or higher, preferably 10 Or more, preferably 15 or more, preferably 20 or more, preferably 25 or more, preferably 30 or more, preferably 35 or more, preferably 40 or more, preferably 45 or more It is characterized by the above low.

Preferred compositions of the present invention are less than 3% by weight, preferably 2% by weight, when the plasticized composition is stored at 70 ° C. for 311 hours in a drying oven as measured by ASTM D1203 using a 0.25 mm thick sheet. Less, preferably less than 1% by weight.

Polyolefin

The NFP described herein is mixed with one or more polyolefins to produce the plasticized compositions of the invention. Preferred polyolefins include propylene polymers and butene polymers.

In one aspect of the invention, the polyolefin is selected from polypropylene homopolymers, polypropylene copolymers, and mixtures thereof. The homopolymer may be a hybrid array polypropylene, isotactic polypropylene, syndiotactic polypropylene, and mixtures thereof. Copolymers are random copolymers, statistical copolymers, block copolymers, and mixtures thereof. In particular, the inventive polymeric mixtures described herein include impact copolymers, elastomers and plastomers, all of which may be physical or in-situ mixtures with polypropylene and / or polybutene. The process for producing polypropylene or polybutene is not critical and is suitable for the polymerization of polyolefins in slurry, solution, gas phase or other suitable methods (e.g. Ziegler-Natta-type catalysts, metals). Sen based catalysts, other suitable catalyst systems or combinations thereof). In a preferred embodiment, the propylene polymer and / or butene polymer are catalysts disclosed in US Pat. Nos. 6,342,566, 6,384,142, WO 03/040201, WO 97/19991, and US Pat. No. 5,741,563, By activator and method. Impact copolymers can likewise be prepared by the methods disclosed in US Pat. Nos. 6,342,566, 6,384,142. Such catalysts are well known in the art and are described, for example, in ZIEGLER CATALYSTS (Gerhard Fink, Rolf Mulhaupt and Hans H. Brintzinger, eds., Springer-Verlag 1995); Resconi et al., Selectivity in Propene Polymerization with Metallocene Catalysts , 100 CHEM. REV. 1253-1345 (2000); And I, II METALLOCENE-BASED POLYOLEFINS (Wiley & Sons 2000).

Preferred propylene homopolymers and copolymers useful in the present invention generally have the following properties:

1. Mw of 30,000 to 2,000,000 g / mol, preferably 50,000 to 1,000,000, more preferably 90,000 to 500,000, as measured by GPC as described below in the test method piece; And / or

2. Mw / Mn of 1 to 40, preferably 1.6 to 20, more preferably 1.8 to 10, more preferably 1.8 to 3, as measured by GPC as described below in the test method piece; And / or

3. Tm of 30 to 200 ° C, preferably 30 to 185 ° C, preferably 50 to 175 ° C, more preferably 60 to 170 ° C, as measured by DSC as described below in the test method piece Melting); And / or

4. Crystallinity of 5 to 80%, preferably 10 to 70%, more preferably 20 to 60%, as measured by DSC as described below in the test method piece; And / or

5. Glass transition temperature (Tg) of -40 to 20 ° C, preferably -20 to 10 ° C, more preferably -10 to 5 ° C, as measured by DMTA as described below in the Test Method piece; And / or

6. Heat of fusion (Hf) of 180 J / g or less, preferably 20 to 150 J / g, more preferably 40 to 120 J / g, as measured by DSC as described below in the Test Method piece; And / or

7. Crystallization temperature (Tc) of 15 to 120 ° C, preferably 20 to 115 ° C, more preferably 25 to 1110 ° C, preferably 60 to 145 ° C, as measured by the method described below in the Test Method piece; And / or

8. Heat deflection temperature of 45 to 140 ℃, preferably 60 to 135 ℃, more preferably 75 to 125 ℃ when measured by the method described below in the test method piece; And / or

9. Rockwell hardness (R scale) of 25 or more, preferably 40 or more, preferably 60 or more, preferably 80 or more, preferably 100 or more, preferably 25 to 125; And / or

10. Crystallinity percentage of at least 30%, preferably at least 40%, optionally at least 50%, as measured by the methods described below in Test Method; And / or

11.As measured by subtracting the crystallinity percentage from 100, at least 50%, optionally at least 60%, optionally at least 70%, alternatively 50 to 95%, or at most 70%, preferably at most 60%, preferably Preferably containing less than 50% amorphous material; And / or

12. A branch number (g ') of 0.2 to 2.0, preferably 0.5 to 1.5, preferably 0.7 to 1.1, as measured by the method described below.

The polyolefin may be a propylene homopolymer. In one embodiment, the propylene homopolymer has a molecular weight distribution (Mw) of not more than 40, preferably 1.5 to 10, 1.8 to 7, in another embodiment, 1.9 to 5 in another embodiment, and 2.0 to 4 in another embodiment. / Mn). In another embodiment, the propylene homopolymer is 20 in-lb to 1000 in-lb in one embodiment, 30 in-lb to 500 in-lb in another embodiment, as measured on a 0.125 inch disk at 23 ° C. In other embodiments, the Gardner impact strength ranges from 40 in-lbs to 400 in-lbs. In another embodiment, the 1% secant flexural modulus is from 100 MPa to 2300 MPa in one embodiment, from 200 MPa to 2100 MPa in another embodiment, from 300 MPa to 2000 MPa in another embodiment, wherein the preferred polyolefin is The combination of arbitrary bending modulus upper and lower limits is shown. The melt flow rate (MFR) (ASTM D 1238, 230 ° C., 2.16 kg) of the preferred propylene polymer is from 0.1 dg / min to 2500 dg / min in one embodiment and from 0.3 to 500 dg / min in another embodiment.

Polypropylene homopolymers or propylene copolymers useful in the present invention may have some isotacticity. Thus, in one embodiment, polyolefins comprising isotactic polypropylene are polymers useful in the present invention, and likewise highly isotactic polypropylene is useful in another embodiment. As used herein, “isotactic” is defined as having at least 10% isotactic fender according to analysis by ¹³ C-NMR as described in the test method below. As described herein, "highly isotactic" is defined as having at least 60% isotactic pentad according to analysis by ¹³ C-NMR. In a preferred embodiment, the polypropylene homopolymer having at least 85% and in still other embodiments at least 90% isotacticity is a polyolefin.

In another preferred embodiment, the polypropylene homopolymer having at least 85% and in still other embodiments at least 90% syndiotacticity is a polyolefin. As used herein, "syndiotacticity" is defined as having at least 10% syndiotactic pentad according to analysis by ¹³ C-NMR as described in the Test Method section below. As used herein, “highly syndiotactic” is defined as having at least 60% syndiotactic pentad according to analysis by ¹³ C-NMR.

In another embodiment, the propylene homopolymer can be isotactic, highly isotactic, syndiotactic, highly syndiotactic or hybrid configuration. Hybrid array polypropylene is defined as less than 10% isotactic or syndiotactic pentad. Preferred hybrid array polypropylenes generally have a Mw of 20,000 to 1,000,000.

Preferred propylene polymers useful in the present invention are ACHIEVE® and ESCORENE® manufactured by ExxonMobil Chemical Company of Houston, Texas.

In another embodiment of the present invention, the polyolefin is selected from propylene derived units and ethylene and C ₄ to C ₂₀ alpha-olefin derived units, in another embodiment from ethylene and C ₄ to C ₁₀ alpha-olefin derived units. Propylene copolymer (random or block) of selected units. Ethylene or C ₄ to C ₂₀ alpha-olefin derived units range from 0.1 to 50 weight percent in one embodiment, 0.5 to 30 weight percent in another embodiment, 1 to 15 weight percent in another embodiment, and another embodiment. In an amount of 0.1 to 5% by weight, wherein the preferred copolymers comprise ethylene and C ₄ to C ₂₀ alpha-olefin derived units in any combination of the upper and lower weight percentages described herein. The propylene copolymer is greater than 8,000 g / mol in one embodiment, greater than 10,000 g / mol in another embodiment, greater than 12,000 g / mol in another embodiment, and greater than 20,000 g / mol in another embodiment. And, in another embodiment, a weight average molecular weight of less than 1,000,000 g / mol, and in another embodiment of less than 800,000 g / mol, wherein the preferred copolymers may include any of the upper and lower molecular weights described herein.

Particularly preferred propylene copolymers have a molecular weight distribution (Mw / Mn) of 1.5 to 10, 1.6 to 7, in another embodiment, 1.7 to 5 in another embodiment, and 1.8 to 4 in another embodiment. Gardner impact strength tested on a 0.125 inch disk at 23 ° C. ranges from 20 in-lb to 1000 in-lb in one embodiment, 30 in-lb to 500 in-lb in another embodiment, and 40 in- in another embodiment. lb to 400 in-lb. In another embodiment, the 1% secant flexural modulus of the propylene copolymer is from 100 MPa to 2300 MPa, in another embodiment from 200 MPa to 2100 MPa, in another embodiment from 300 MPa to 2000 MPa, wherein the preferred polyolefin is The combination of arbitrary bending modulus upper and lower limits is shown. The melt flow rate (MFR) (ASTM D 1238, 230 ° C., 2.16 kg) of the propylene copolymer is from 0.1 dg / min to 2500 dg / min in one embodiment and from 0.3 to 500 dg / min in another embodiment.

In another embodiment, the polyolefin is a propylene and ethylene and a C ₄ to C ₂₀ linear, branched or cyclic monomer, in another embodiment a C ₄ to C ₁₂ linear or branched alphaolefin, preferably butene, pentene, At least one other monomer selected from the group consisting of hexene, heptene, octene, nonene, decene, dodecene, 4-methylpentene-1, 3-methylpentene-1, 3,5,5-trimethyl-hexene-1 and the like; It is a propylene copolymer containing. The monomer is present at 50% by weight or less, preferably 0 to 40% by weight, more preferably 0.5 to 30% by weight, more preferably 2 to 30% by weight, more preferably 5 to 20% by weight.

In a preferred embodiment, the butene homopolymers and copolymers of the invention generally have the following properties:

1. Mw of 30,000 to 2,000,000 g / mol, preferably 50,000 to 1,000,000, more preferably 90,000 to 500,000, as measured by GPC as described below in the test method piece; And / or

2. Mw / Mn of 1 to 40, preferably 1.6 to 20, more preferably 1.8 to 10, more preferably 1.8 to 3, as measured by GPC as described below in the test method piece; And / or

3. a Tm (second melt) of 30 to 150 ° C, preferably 30 to 145 ° C, preferably 50 to 135 ° C, as measured by DSC as described below in the Test Method piece; And / or

4. Crystallinity of 5 to 80%, preferably 10 to 70%, more preferably 20 to 60%, as measured by DSC as described below in the test method piece; And / or

5. Glass transition temperature (Tg) of -50 ° C to 0 ° C, as measured by DMTA, as described below in the Test Method piece; And / or

6. Heat of fusion (Hf) of 180 J / g or less, preferably 20 to 150 J / g, more preferably 40 to 120 J / g, as measured by DSC as described below in the Test Method piece; And / or

7. Crystallization temperature (Tc) of 10 to 130 ° C, preferably 20 to 115 ° C, more preferably 25 to 110 ° C, preferably 60 to 145 ° C, as measured by the method described below in the Test Method piece; And / or

8. As measured by subtracting the crystallinity percentage from 100, at least 50%, optionally at least 60%, optionally at least 70%, optionally at 50-95%, or at most 70%, preferably at most 60%, preferably Preferably containing less than 50% amorphous material; And / or

9. A branching index (g ') of 0.2 to 2.0, preferably 0.5 to 1.5, preferably 0.7 to 1.1, as measured by the method described below.

Preferred linear alpha-olefins useful as comonomers for propylene copolymers useful in the present invention are C ₃ to C ₈ alpha-olefins, more preferably 1-butene, 1-hexene and 1-octene, more preferably 1- Contains butenes. Preferred linear alpha-olefins useful as comonomers for the butene copolymers useful in the present invention include C ₃ to C ₈ alpha-olefins, more preferably propylene, 1-hexene and 1-octene, more preferably propylene. . Preferred branched alpha-olefins include 4-methyl-1-pentene, 3-methyl-1-pentene and 3,5,5-trimethyl-1-hexene, 4-ethyl-1-nonene. Preferred aromatic group-containing monomers contain up to 30 carbon atoms. Suitable aromatic group-containing monomers comprise one or more aromatic structures, preferably 1 to 3, more preferably phenyl, indenyl, fluorenyl, or naphthyl moieties. The aromatic group-containing monomer further contains one or more polymerizable double bonds such that after polymerization, the aromatic structure can be suspended from the polymer backbone. Aromatic group containing monomers may be further substituted with one or more hydrocarbon groups including, but not limited to, C1 to C10 alkyl groups. Additionally two adjacent substituents are joined to form a ring structure. Preferred aromatic group-containing monomers contain at least one aromatic structure attached to the polymerizable olefin moiety. Particularly preferred aromatic monomers are styrene, alpha-methylstyrene, para-alkylstyrene, vinyltoluene, vinylnaphthalene, allyl benzene and indene, in particular styrene, paramethyl styrene, 4-phenyl-1-butene and allyl benzene It includes.

Non-aromatic cyclic group-containing monomers are also preferred. These monomers contain up to 30 carbon atoms. Suitable non-aromatic cyclic group-containing monomers preferably have one or more polymerizable olefinic groups that run on or are part of the cyclic structure. The cyclic structure may also be further substituted by one or more hydrocarbon groups, including but not limited to C1 to C10 alkyl groups. Preferred non-aromatic cyclic group-containing monomers include vinylcyclohexane, vinylcyclohexene, vinylnorbornene, ethylidene norbornene, cyclopentadiene, cyclopentene, cyclohexene, cyclobutene, vinyladamantane and the like. do.

Preferred diolefin monomers useful in the present invention include any hydrocarbon structure having at least two unsaturated bonds, preferably C4 to C30, wherein at least two of the unsaturated bonds are formed by stereospecific or nonstereospecific catalysts. Easily mixed into the polymer. It is further preferred that the diolefin monomers are selected from alpha, omega-diene monomers (ie di-vinyl monomers). More preferably, the diolefin monomer is a linear di-vinyl monomer, most preferably a monomer having 4 to 30 carbon atoms. Examples of preferred dienes include butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetra Decadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, aikosadiene, henecosadaiene, docosadiene, tricosadiene, tetracosa Dienes, pentacosadienes, hexacosadienes, heptacosadienes, octacosadienes, nonacosadienes, triacontadienes, and particularly preferred dienes are 1,6-heptadienes, 1 , 7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, and low molecular weight polybutadiene (less than Mw 1000 g / mol). Preferred cyclic dienes include cyclopentadiene, vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene, dicyclopentadiene or higher rings with or without substituents at various ring positions.

In a preferred embodiment, the at least one diene is at most 10% by weight, preferably 0.00001 to 1.0% by weight, preferably 0.002 to 0.5% by weight, more preferably based on the total weight of the composition in the polymers produced herein. Present in 0.003 to 0.2% by weight. In some embodiments, up to 500 ppm, preferably up to 400 ppm, preferably up to 300 ppm of diene is added to the polymerization. In another embodiment, at least 50 ppm, or at least 100 ppm, or at least 150 ppm diene is added to the polymerization.

In another embodiment, the Gardner impact strength tested on a 0.125 inch disk at 23 ° C. of the butene copolymer is from 20 in-lb to 1000 in-lb, in another embodiment from 30 in-lb to 500 in-lb, another In embodiments it ranges from 40 in-lb to 400 in-lb. In addition, the butene copolymer has a 1% secant flexural modulus of 100 MPa to 2300 MPa, in another embodiment 200 MPa to 2100 MPa, and in another embodiment 300 MPa to 2000 MPa, wherein the preferred polyolefin is any flex The combination of modulus upper limit and lower limit is shown. The melt flow rate (MFR) (ASTM D 1238, 230 ° C.) of the preferred copolymer is from 0.1 dg / min to 2500 dg / min in one embodiment and from 0.1 to 500 dg / min in another embodiment.

In another embodiment, the propylene copolymer is a random copolymer, also known as "RCP" comprising propylene and up to 20 mol% ethylene or C ₄ to C ₂₀ olefins, preferably up to 20 mol% ethylene.

In another embodiment, the polyolefin is an impact copolymer (ICP) or block copolymer. Propylene impact copolymers are commonly used in applications where strength and impact resistance are desired, such as molded and extruded automotive parts, appliances, bags and furniture. Propylene homopolymers alone are often undesirable for this use, especially because they are too fragile and have low impact resistance, especially at low temperatures, while propylene impact copolymers are carefully crafted for this purpose.

Typical propylene impact copolymers contain two or more phases or components such as homopolymer components and copolymer components. The impact copolymer also includes three phases, such as the PP / EP / PE combination, with PP as the dispersed phase with EP outside the continuous and dispersed phase particles and PE inside. These components are typically prepared by a sequential polymerization process wherein the homopolymer produced in the first reactor is transferred to the second reactor where a copolymer is produced and incorporated into the matrix of homopolymer components. The copolymer component has rubber properties and provides the desired impact resistance, while the homopolymer component provides total stiffness.

Another important feature of the ICP is the amount of amorphous polypropylene they contain. The ICPs of the present invention are low amorphous polypropylenes, preferably less than 3% by weight, more preferably less than 2% by weight, more preferably less than 1% by weight, and most preferably there is no measurable amount. It is characterized by having propylene. The percentage of amorphous polypropylene is measured by the method described below in the Test Method.

Preferred impact copolymers may be reactor mixtures (same system mixtures) or post reactor (other reaction system) mixtures. In one embodiment, a suitable impact copolymer comprises from 40 to 95% by weight of component A and from 5 to 60% by weight of component B, based on its total weight, wherein component A is a propylene homopolymer or ethylene, butene, hexene or octene balls A copolymer comprising up to 10 weight percent monomer, component B comprising from 5 to 70 weight percent ethylene, butene, hexene and / or octene comonomer, and from about 95 weight percent propylene to about 30 weight percent propylene Copolymers. In one embodiment of the impact copolymer, component B consists essentially of about 30 to about 65 weight percent of propylene and ethylene. In another embodiment, component B is an ethylene-propylene copolymer, ethylene-propylene-diene terpolymer, ethylene-acrylate copolymer, ethylene-vinyl acetate, styrene-butadiene copolymer, ethylene-acrylic ester Copolymers, polybutadienes, polyisoprene, natural rubber, isobutylene, hydrocarbon resins, where hydrocarbon resins have a molecular weight of less than 5000, a Tg of about 50 to 100 ° C and less than about 140 ° C as measured by ASTM E-28 A softening point, Ring and Ball), rosin esters, and mixtures thereof. In another embodiment, component B has a molecular weight distribution of less than 3.5. In another embodiment, component B has a molecular weight distribution of at least 20,000. Useful impact copolymers are disclosed in US Pat. Nos. 6,342,566 and 6,384,142.

Component B is most preferably a copolymer consisting essentially of propylene and ethylene, but other propylene copolymers, ethylene copolymers or terpolymers may be suitable depending on the particular product properties desired. For example, propylene / butene, hexene or octene copolymers, and ethylene / butene, hexene or octene copolymers may be used, and propylene / ethylene / hexene-1 terpolymers may be used. In a preferred embodiment, component B is a copolymer comprising at least 40% by weight propylene, more preferably from about 80% to about 30% by weight of propylene, more preferably from about 70% to about 35% by weight propylene. The content of comonomer of component B is preferably about 20 to about 70 weight percent, more preferably about 30 to about 65 weight percent comonomer, more preferably about 35 to about 60 weight percent comonomer. Most preferably, component B consists essentially of propylene and from about 20 to about 70% ethylene, more preferably from about 30 to about 65% ethylene, most preferably from about 35 to about 60% ethylene.

For other component B copolymers, the comonomer content needs to be adjusted depending on the intended specific properties. For example, for ethylene / hexene copolymers, component B should contain at least 17% by weight of hexene, and at least 83% by weight of ethylene.

Component B, preferably narrow molecular weight distribution Mw / Mn (“MWD”), ie less than 5.0, preferably less than 4.0, more preferably less than 3.5, more preferably less than 3.0, most preferably less than 2.5 It has a narrow molecular weight distribution. These molecular weight distributions should be obtained in the absence of bisbreaking or peroxide or other post-reactor treatment molecular weight control methods. Component B preferably has a weight average molecular weight (Mw measured by GPC) of at least 100,000, preferably at least 150,000, most preferably at least 200,000.

Component B preferably has an intrinsic viscosity greater than 1.00 dl / g, more preferably an intrinsic viscosity greater than 1.50 dl / g and most preferably an intrinsic viscosity greater than 2.00 dl / g. The term "intrinsic viscosity" or "IV" is used herein to mean the viscosity of a solution of a polymer, such as component B in a given solvent, at a given temperature, typically when the polymer composition is an infinite diluent. According to ASTM Standard Test Method D 1601-78, the IV measurement method relates to a standard capillary viscosity measuring device, where the viscosity of a series of concentrations of polymer in a solvent is measured at a given temperature. For component B, decalin is a suitable solvent and a typical temperature is 135 ° C. From the viscosity values of solutions of various concentrations, the "value" in infinite dilution can be determined by extrapolation.

Component B is preferably greater than 60%, more preferably greater than 65%, more preferably greater than 70%, more preferably greater than 75%, more preferably greater than 80%, even more preferred Has a composition distribution width index (CDBI) of greater than 85%. CDBI defines compositional changes in the polymer as a whole in terms of the ethylene (or other monomer) content of the copolymer. The measurement of the composition distribution is the "Composition Distribution Width Index (" CDBI ")" as defined in US Pat. No. 5,382,630, which is incorporated herein by reference. CDBI is defined as the percentage of copolymer molecular weight that has a comonomer content within 50% of the average total molar comonomer content. The CDBI of the copolymer is readily determined using well known techniques for isolating individual fractions of samples of the copolymer. Such techniques are described in Wild et al . , J. Poly. Sci., Poly. Phys. Ed. , vol. 20, p. 441 (1982) and US Pat. No. 5,008,204, Temperature Rising Elution Fraction (TREF).

Component B of ICP 'preferably has a low crystallinity, preferably less than 10% by weight of the crystalline portion, more preferably less than 5% by weight of the crystalline portion. Where the crystalline portion of component B is present, its composition is preferably the same or at least similar (within 15% by weight) to the rest of component B in terms of total comonomer weight percent.

The preferred melt flow rate (“MFR”) of this ICP depends on the desired end use but is generally about 0.2 dg / min to about 200 dg / min, more preferably about 5 dg / min to about 100 dg / min. . Importantly, high MFR, i.e. higher than 50 dg / min can be obtained. The ICP preferably has a melting point (Tm) of at least 145 ° C, preferably at least 150 ° C, more preferably at least 152 ° C, most preferably at least 155 ° C.

ICP comprises about 40 to about 95 weight percent of component A and about 5 to about 60 weight percent of component B, preferably about 50 to about 95 weight percent of component A and about 5 to about 50 percent of component B, more preferably Preferably from about 60 to about 90 weight percent of component A and from about 10 to about 40 weight percent of component B. In the most preferred embodiment, the ICP consists essentially of components A and B. The total comonomer (preferably ethylene) content of the total ICP is preferably from about 2 to about 30 weight percent, preferably from about 5 to about 25 weight percent, more preferably from about 5 to about 20 weight percent, more preferably Preferably from about 5 to about 15 weight percent comonomer.

In another embodiment, the preferred impact copolymer compositions have component A and component B in which their respective refractive indices (measured by ASTM D 542-00) are within 20% of each other, preferably within 15%, preferably Selected to be within 10%, more preferably within 5% of each other. This selection produces an impact copolymer with good transparency. In another embodiment, the preferred impact copolymer composition comprises a mixture of component A and NFP and a mixture of component B and NFP, wherein the refractive index of the mixtures (measured by ASTM D 542-00) is within 20% of each other, Preferably 15%, preferably 10%, more preferably 5%.

In another embodiment, the Gardner impact strength tested on a 0.125 inch disk at −29 ° C. of the propylene impact copolymer ranges from 20 in-lb to 1000 in-lb in one embodiment, and 30 in-lb to 500 in another embodiment. in-lb, in another embodiment from 40 in-lb to 400 in-lb. In addition, the 1% secant flexural modulus of the propylene impact copolymer is 100 MPa to 2300 MPa in one embodiment, 200 MPa to 2100 MPa in another embodiment, and 300 MPa to 2000 MPa in another embodiment, with the preferred polyolefins Can represent any of the bending modulus upper and lower limits. The melt flow rate (MFR) (ASTM D 1238, 230 ° C., 2.16 kg) of the preferred homopolymer is from 0.1 dg / min to 2500 dg / min in one embodiment and from 0.3 to 500 dg / min in another embodiment.

Still other suitable polyolefins include polypropylene homopolymers or mixtures of propylene copolymers and plastomers. Plastomers useful in the present invention are 0.85 to 0.915 g / cm ³ ASTM D 4703 Method B and ASTM D 1505-first method are compression molding at a cooling rate of 15 ° C./min and the second is density measurement and 0.10 to 30 dg / min. Gradient density column method (ASTM D 1238; 190 ° C., 2.1 kg) for the melt index (MI). In one embodiment, a useful plastomer is a copolymer of ethylene derived units and one or more C ₃ to C ₁₀ alpha-olefin derived units, which copolymers have a density of less than 0.915 g / cm ³ . The amount of comonomer (C ₃ to C ₁₀ alphaolefin derived units) present in the plastomer is 2 to 35% by weight in one embodiment, 5 to 30% by weight in another embodiment, 15 to 15 in another embodiment. 25 weight percent, in another embodiment 20-30 weight percent.

Plastomers useful in the present invention have a melt index (MI) of 0.10 to 20 dg / min in one embodiment, 0.2 to 10 dg / min in another embodiment and 0.3 to 8 dg / min in another embodiment. The average molecular weight of useful plastomers is from 10,000 to 800,000 in one embodiment and from 20,000 to 700,000 in another embodiment. The 1% secant flexural modulus (ASTM D 790) of the useful plastomers is from 10 MPa to 150 MPa in one embodiment and from 20 MPa to 100 MPa in another embodiment. In addition, the plastimers useful in the compositions of the present invention are in one embodiment 30 to 80 ° C. (first melt peak) and 50 to 125 ° C. (second melt peak), and in another embodiment 40 to 70 ° C. (first melt) Peak) and a melting point (Tm) of 50 to 100 ° C (second melt peak).

Plastomers useful in the present invention are metallocene catalyzed copolymers of ethylene derived units and higher alpha-olefin derived units such as propylene, 1-butene, 1-hexene and 1-octene, which are one or more of these Sufficient amount of comonomer units is provided to yield a density of 0.860 to 0.900 g / cm ³ in one embodiment. The molecular weight distribution (Mw / Mn) of the preferred plastomers is 1.5 to 5 in one embodiment and 2.0 to 4 in another embodiment. Examples of commercially available plastomers are EXACT 4150, copolymers of ethylene and 1-hexene or EXACT 8201, copolymers of ethylene and 1-octene, wherein the 1-hexene derived units comprise 18-22% by weight of plastomer And had a density of 0.895 g / cm ³ and an MI of 3.5 dg / min (ExxonMobil Chemical Company, Houston, TX), the 1-octene derived units comprised 26-30% by weight of the plastomer And a density of 0.882 g / cm ³ and an MI of 1.0 dg / min (ExxonMobil Chemical Company, Houston, TX).

In another embodiment, the polymers useful in the present invention include heat of fusion measured by differential scanning calorimetry (DSC) of less than 50 J / g, melt index (MI) of less than 20 dg / min, and / or 20 dg. homopolymers and random copolymers of propylene having an MFR of / min or less and have stereoregular propylene crystallinity, preferably isotactic stereoregular propylene crystallinity. In one embodiment, the polymer is a random copolymer of propylene and one or more comonomers selected from ethylene, C ₄ -C ₁₂ alpha-olefins and combinations thereof. Preferably, the random copolymer of propylene comprises 2 to 25% by weight polymerized ethylene units based on the total weight of the polymer, has a narrow compositional distribution and has a melting point (Tm) of 25 to 120 ° C, or 35 to 80 ° C. Have a heat of fusion in the range having an upper limit of 50 to 25 J / g and a lower limit of 1 to 3 J / g, a molecular weight distribution (Mw / Mn) of 1.8 to 4.5, and less than 20 dg / min, or 15 dg / min It has a melt index (MI) of less than. The intermolecular composition distribution of the copolymer is measured by thermal fractionation in a solvent. Typical solvents are saturated hydrocarbons such as hexane or heptane. The thermal fractionation procedure is described below. Generally approximately 75%, preferably 85%, by weight of the copolymer is isolated as one or two adjacent soluble fractions and the remainder of the copolymer is the fraction immediately preceding or following. Each of these fractions comprises a composition (weight percent of comonomer such as ethylene or other alphaolefins) having a difference of 20% or less (relative), preferably 10% (relative), of the average weight percent of comonomer of the copolymer. Have The copolymer has a narrow compositional distribution if it satisfies the fractionation test described above.

Particularly preferred polymers useful in the present invention are elastomeric polymers having normal levels of crystallinity due to stereoregular propylene sequences. Such polymers include (A) propylene homopolymers whose stereoregularity is disrupted in some manner, such as regio-inversions; (B) a random propylene copolymer in which said propylene stereoregularity is at least partially disrupted by comonomers; Or (C) a combination of (A) and (B).

In one embodiment, the polymer further comprises a non-conjugated diene monomer to aid in vulcanization and other chemical modification of the mixture composition. The amount of diene present in the polymer is preferably less than 10% by weight, more preferably less than 5% by weight. The diene may be any non-conjugated diene commonly used for vulcanization of ethylene propylene rubber, including but not limited to ethylidene norbornene, vinyl norbornene, and dicyclopentadiene.

In one embodiment, the polymer is a random copolymer of propylene and one or more comonomers selected from ethylene, C ₄ -C ₁₂ α-olefins, and combinations thereof. In certain embodiments of this embodiment, the copolymer has a lower limit of 20%, 25%, or 28% by weight of 2%, 5%, 6%, 8%, or 10% by weight of the ethylene-derived unit. It contains by the upper limit of weight%. This embodiment also provides a lower limit of 72 weight percent, 75 weight percent, or 80 weight percent to 98 weight percent, 95 weight percent, 94 weight percent, 92 weight percent, or 90 weight percent of the propylene-derived units present in the copolymer. Include in the amount of the upper limit of%. These percentages are based on the total weight of propylene and ethylene-derived units. That is, based on the sum of the weight percent of propylene-derived units and ethylene-derived weight percent of 100%. The ethylene composition of the polymer is measured as follows. The thin homogeneous film is compressed at a temperature greater than about 150 ° C. and immobilized on a Perkin Elmer PE 1760 infrared spectrophotometer. Record the full spectrum of the sample from 600 cm ⁻¹ to 4000 cm ⁻¹ and calculate the monomer weight percent of ethylene according to the following equation:

Ethylene Weight% = 82.585-111.987X + 30.045 X ²

Where

X is the ratio of the higher of the peak height at 1155 cm ⁻¹ and the peak height at 722 cm ⁻¹ or 732 cm ⁻¹ .

The concentration of other monomers in the polymer can also be measured using this method.

The comonomer content of discontinuous molecular weight can be measured by Fourier Transform Infrared Spectroscopy (FTIR) with the samples collected by GPC. One such method is described in Wheeler and Willis, Applied Spectroscopy, 1993, vol. 47, pp. 1128-1130. Different but similar methods serve equally for this purpose and are well known to those skilled in the art.

The comonomer content and sequence distribution of the polymer can be determined by ¹³ C nuclear magnetic resonance ( ¹³ C NMR), which methods are well known to those skilled in the art.

In one embodiment, the polymer is a random propylene copolymer with a narrow composition distribution. In another embodiment, the polymer is a random propylene copolymer having a narrow composition distribution and a melting point of 25 to 110 ° C. Such copolymers are described as random in the case of polymers comprising propylene, comonomers, and optionally dienes, since the number and distribution of comonomer residues are compatible with random statistical polymerization of monomers. In the stereoblock structure, the number of any mutually adjacent block monomer residues is more than predicted from the statistical distribution in random copolymers having similar compositions. Existing ethylene-propylene copolymers having a stereoblock structure have a distribution of ethylene moieties that are compatible with these block structures rather than a random statistical distribution of monomer residues in the polymer. The intramolecular composition distribution (ie randomness) of the copolymer can be determined by ¹³ C NMR, which locates the comonomer residues relative to neighboring propylene residues. The intermolecular composition distribution of the copolymer can be measured by thermal fractionation in a solvent. Typical solvents are saturated hydrocarbons such as hexane or heptane. Generally approximately 75%, preferably 85%, by weight of the copolymer is isolated as one or two adjacent soluble fractions, with the remainder of the copolymer being the fraction immediately preceding or following. Each of these fractions comprises a composition (weight percent of comonomer such as ethylene or other alphaolefins) having a difference of 20% or less (relative), preferably 10% (relative), of the average weight percent of comonomer of the copolymer. Have The copolymer has a narrow compositional distribution if it satisfies the fractionation test described above. To prepare a copolymer with the intended randomness and narrow composition, (1) a single-site metallocene catalyst is used that allows only an additional single statistical mode of the first and second monomer sequences and (2) the copolymer is a copolymer. It is advantageous if well mixed in a continuous flow stirred bath polymerization reactor that allows only a single polymerization environment for substantially all of the polymer chains.

The crystallinity of the polymer can be expressed in terms of heat of fusion. Embodiments of the present invention include polymers having a heat of fusion measured by DSC in the range of 1.0 J / g, or lower limit of 3.0 J / g to 50 J / g, or upper limit of 10 J / g. Without wishing to be bound by theory, it is believed that the polymers of embodiments of the invention generally have isotactic crystalline propylene sequences and the heat of fusion is due to the melting of these crystalline fragments.

The crystallinity of the polymer is expressed as percent crystallinity. The highest thermal energy of polypropylene is estimated as 207 J / g. In other words, the 100% crystallinity is equal to 207 J / g. Preferably, the polymer has a polypropylene crystallinity ranging from an upper limit of 65%, 40%, 30%, 25%, or 20% to a lower limit of 1%, 3%, 5%, 7%, or 8%.

The level of crystallinity is also reflected in the melting point. The term "melting point" as used herein means the highest peak, meaning the highest amount of polymer, as discussed above, as opposed to the peak occurring at the highest temperature of the primary and secondary melting peaks as measured by DSC. In one embodiment of the invention, the polymer has a single melting point. In general, a sample of propylene copolymer will show a secondary melting peak adjacent to the primary peak, which is considered together as a single melting point. The highest of these peaks is considered to be the melting point. The polymer is preferably by DSC between an upper limit of 110 ° C, 105 ° C, 90 ° C, 80 ° C, or 70 ° C to a lower limit of 0 ° C, 20 ° C, 25 ° C, 30 ° C, 35 ° C, 40 ° C or 45 ° C. It has a melting point.

Such polymers used in the present invention have a weight average molecular weight (Mw) ranging from an upper limit of 5,000,000 g / mol, 1,000,000 g / mol or 500,000 g / mol to a lower limit of 10,000 g / mol, 20,000 g / mol or 80,000 g / mol. And the molecular weight distribution Mw / Mn (MWD) is also sometimes referred to as the "polydispersity index" (PDI) and has a lower limit of 1.5, 1.8 or 2.0 to an upper limit of 40, 20, 10, 5 or 4.5. In one embodiment, the polymer has a Mooney viscosity, ML (1 + 4) @ 125 ° C. of 100 or less, 75 or less, 60 or less, or 30 or less. Pattern viscosity, as used herein, is measured as ML (1 + 4) at 125 ° C. according to ASTM D1646 unless otherwise indicated.

Polymers used in embodiments of the present invention may have a stereoregularity index (m / r) in the range of a lower limit of 4 or 6 to an upper limit of 8, 10 or 12. As used herein, the stereoregularity index expressed in “m / r” is determined by ¹³ C nuclear magnetic resonance (NMR). The stereoregularity index of m / r is calculated as defined herein by HN Cheng, Macromolecules , 17, 1950 (1984). The symbol "m" or "r" is a stereochemistry of a pair of adjacent propylene groups, where "m" represents meso and "r" represents racemic. M / r ratios of 0 to less than 1.0 generally represent syndiotactic polymers, m / r ratios of 1.0 represent hybrid array materials, and m / r ratios greater than 1.0 represent isotactic materials. Isotactic materials can theoretically have a ratio close to infinity, and many byproduct hybrid array polymers have a sufficient isotactic content, resulting in proportions greater than 50.

In one embodiment, the polymer has isotactic stereoregular propylene crystallinity. As used herein, “stereoregularity” refers to the dominant number of polypropylene or polypropylene continuous phases of a blend, eg, impact copolymers excluding any other monomers such as ethylene, i. With two insertions it is meant that the stereochemical orientation of the pendant methyl group is the same in meso or racemic.

An additional procedure for describing the stereoregularity of the propylene units of embodiments of the present invention is the use of ternary stereoregularity. The triad stereoregularity of the polymer is the relative stereoregularity of the sequence of three adjacent propylene units, and the chain consists of head to tail bonds and is expressed as a binary combination of m and r sequences. Copolymers of the invention are typically expressed as the ratio of the number of stereoregular units specified for all of the propylene triads in the copolymer.

Ternary stereoregularity (mm fraction) of the propylene copolymer is determined from the ¹³ C NMR spectrum of the propylene copolymer as shown in Equation 2 below.

Where

PPP (mm), PPP (mr) and PPP (rr) represent the peak regions derived from the methyl group of the second unit in the next three propylene unit chains consisting of head-to-tail bonds:

¹³ C NMR spectra of propylene copolymers are measured as disclosed in US Pat. No. 5,504,172. The spectrum associated with the methyl carbon region (19-23 ppm) can be divided into a first region (21.2-21.9 ppm), a second region (20.3-21.0 ppm) and a third region (19.5-20.3 ppm). Each peak in the spectrum was designated by reference to an article in the journal Polymer, Volume 30 (1989), page 1350. In the first region, the methyl group of the second unit in the three propylene unit chains expressed in PPP (mm) resonates. In the second region, the methyl group of the second unit resonates in the three propylene unit chains represented by PPP (mr), and the methyl group (PPE-methyl group) of the propylene unit whose adjacent units are the propylene unit and the ethylene unit (20.7). near ppm). In the third region, the methyl group of the second unit in the three chains of propylene units represented by PPP (rr) resonates, and the methyl group (EPE-methyl group) of propylene whose adjacent units are ethylene units (near 19.8 ppm) .

The calculation of triad stereoregularity is outlined in the technique shown in US Pat. No. 5,504,172. 3 propylene units consisting of a head-to-tail bond, subtracting the peak area for error in the propylene insert (both 2, 1 and 1, 3) from the peak area from the total peak area of the second and third regions Peak areas based on chains (PPP (mr) and PPP (rr)) can be obtained. Thus, the peak areas of PPP (mm), PPP (mr) and PPP (rr) can be calculated and the triad stereoregularity of the propylene unit chain consisting of head-to-tail bonds can be measured.

The polymers of embodiments of the invention have at least 75%, at least 80%, at least 82%, at least 85%, or at least 90% of triad stereoregularity of three propylene units measured by C ¹³ NMR.

In an embodiment of the invention, the polymer has a melt index (MI) of 20 dg / min or less, 7 dg / min or less, 5 dg / min or less, or 2 dg / min or less, or 2 dg / min or less. Measurement of the MI of the polymer is in accordance with ASTM D1238 (190 ° C., 2.16 kg). In this version of the method a portion of the extruded sample is collected and weighed during the test. This is commonly referred to as variant 1 of the experimental procedure. Sample analysis is performed at 190 ° C. after 1 minute warm up on the sample to provide normal temperature for the duration of the experiment.

In one embodiment, the polymers used in the present invention are described in "Second Polymer Component (SPC)", WO 00/69963, WO 00/01766, WO 99/07788, WO WO 02/083753, and also in detail in WO 00/01745 "Propylene Olefin Copolymer", all of which are incorporated herein by reference in their entirety for the execution of US patents. Quote.

Polyolefins suitable for use in the present invention may exist in any physical form when used for mixing with the NFP of the present invention. In one embodiment, reactor granules defined as granules of polymer isolated from the polymerization reactor prior to any processing procedure may be mixed with the NFP of the present invention. The reactor granules have an average diameter of 50 μm to 10 mm in one embodiment and 10 μm to 5 mm in another embodiment. In another embodiment, the polyolefin is in the form of pellets having an average diameter of 1 to 10 mm formed from melt extrusion of reactor granules.

In one embodiment of the present invention, suitable polyolefins for the composition exclude physical mixtures of other polyolefins with polypropylene, and in particular exclude physical mixtures of polypropylene with low molecular weight (500 to 10,000 g / mol) polyethylene or polyethylene copolymers. This is because the low molecular weight polyethylene or polyethylene copolymer is any amount in the polyolefin composition (e.g. polypropylene homopolymer or copolymer) of the present invention, for example as in WO 01/18109 A1. Means not added intentionally.

In a preferred embodiment, the NFP is isoparaffin comprising C ₆ to C ₂₅ isoparaffins. In another embodiment, the non-functionalized plasticizer is a polyalphaolefin comprising C ₁₀ to C ₁₀₀ n-paraffins. Polyolefins can be polypropylene homopolymers, copolymers, impact copolymers, or mixtures thereof, and include plastomers. Non-limiting examples of preferred products made from the compositions of the present invention include films, sheets, fibers, woven fabrics and nonwoven fabrics, tubes, pipes, automotive components, furniture, sports equipment, food storage containers, transparent and translucent products, toys , Plumbing and pipes, and medical equipment. The composition of the present invention is characterized by having an improved (reduced) Tg compared to the starting polyolefin while maintaining other desirable properties.

The polyolefins and NFP can be mixed by any suitable method and are generally mixed to obtain a homogeneous, single phase mixture. For example, it may be mixed in a tumbler, static mixer, batch mixer, extruder, or a combination thereof. The mixing step may occur in the extruder, for example on injection molding marching or on a fiber line as part of the processing method used to produce the product.

The improved properties of the plasticized polyolefin compositions described herein include transparent products (such as cooking and storage utensils), and furniture, automotive components, toys, sportswear, medical devices, sterile medical devices and sterile containers, nonwoven fibers and nonwovens. Fabrics and products made therefrom (e.g. drapes, gowns, filters, hygiene products, diapers and films, oriented films, sheets, tubes, pipes and ductility, high impact strength, and other products where impact strength is below freezing point) It is useful for a variety of applications, including other products such as Processing of the plasticized polyolefins of the present invention to form these products include injection molding, extrusion, thermoforming, blow molding, rotational molding, spunbonding, melt blowing, fiber spinning, blown films, stretching for oriented films, and other conventional methods. It can be carried out by a phosphorus processing method.

In one embodiment of the present invention, conventional plasticizers commonly used for poly (vinyl chloride) are substantially free. In particular, plasticizers such as phthalates, adipates, trimellitate esters, polyesters and other publications (US Pat. No. 3,318,835; No. 4,409,345; International Publication No. WO 02/31044 A1; And PLASTICS ADDITIVES 499-504 (Geoffrey Pritchard, ed., Chapman & Hall 1998) are substantially free of functionalized plasticizers. By "substantially free" is meant that these compounds are not intentionally added to the composition and, if present, are present at less than 0.5% by weight.

In further embodiments, oils such as naphthenes and other aromatic containing oils are present in less than 0.5 of the compositions of the present invention. In addition, aromatic residues and carbon-carbon unsaturations are substantially free of non-functionalized plasticizers used in the present invention in another embodiment. An aromatic moiety includes the compound whose molecule has ring structure characteristics, such as benzene, naphthalene, phenanthrene, anthracene, and the like. By "substantially free" is meant that these aromatic compounds or moieties are not intentionally added to the composition and, if present, are present at less than 0.5% by weight.

In another embodiment of the composition of the present invention, there is substantially no "compatibility agent" such as conventional plasticizers, elastomers or low molecular weight polyethylene. In particular, ethylene homopolymers and copolymers having a weight average molecular weight of 500 to 10,000 are substantially free. Such polyethylene compatibilizers are for example disclosed in WO 01/18109 A1. "Substantially free" means that these compounds are not intentionally added to the composition and, if present, are less than 5%, more preferably less than 4%, more preferably based on the weight of the polyolefin, ethylene polymer or copolymer and NFP Preferably less than 3% by weight, more preferably less than 2% by weight, more preferably less than 1% by weight, more preferably less than 0.5% by weight.

Mixing and product

The polyolefin composition of the present invention may contain other additives. These additives include antioxidants, nucleating agents, acid scavengers, stabilizers, preservatives, blowing agents, other UV absorbers (such as chain-breaking antioxidants), quenching agents, antistatic agents, slip agents, pigments, dyes and fillers. And curing agents such as peroxides. Dyestuffs and other colorants conventional in the industry are present in amounts of 0.01 to 10% by weight in one embodiment and 0.1 to 6% by weight in another embodiment. Suitable nucleating agents are described, for example, in HNBeck, Heterogeneous Nucleating Agents for Polypropylene Crystallization , 11 J. APPLIED POLY. SCI. 673-685 (1967) and Heterogeneous Nucleation Studies on Polypropylene, 21 J. POLY. SCI .: POLY. LETTERS 347-351. Examples of suitable nucleating agents include sodium benzoate, sodium 2,2'-methylenebis (4,6-di-t-butylphenyl) phosphate, aluminum 2,2'-methylenebis (4,6-di-t-butylphenyl ) Phosphate, dibenzylidene sorbitol, di (p-tollylidene) sorbitol, di (p-ethylbenzylidene) sorbitol, bis (3,4-dimethylbenzylidene) sorbitol, and N ', N'-di Salts of cyclohexyl-2,6-naphthalenedicarboxamide, and disproportionated rosin esters. The foregoing is intended to illustrate the proper selection of nucleating agents for inclusion in the present polypropylene blend.

In particular, antioxidants and stabilizers such as organic phosphites, hindered amines and phenolic antioxidants, in one embodiment are 0.001 to 2% by weight in the polyolefin composition of the invention, in another embodiment 0.01 to 0.8% by weight, and In other embodiments, from 0.02 to 0.5% by weight. Non-limiting examples of suitable organic phosphites include tris (2,4-di-t-butylphenyl) phosphite (IRGAFOS 168) and di (2,4-di-t-butylphenyl) pentaerythritol diphosphite (ULTRANOX) 626). Non-limiting examples of hindered amines include poly [2-N, N'-di (2,2,6,6-tetramethyl-4-piperidinyl) -hexanediamine-4- (1-amino-1, 1,3,3-tetramethylbutane) sim-triazine] (CHIMASORB 944); Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (TINUVIN 770). Non-limiting examples of phenolic antioxidants include pentaerythritol tetrakis (3,5-di-t-butyl-4-hydroxyphenyl) propionate (IRGANOX 1010); And 1,3,5-tri (3,5-di-t-butyl-4-hydroxybenzyl-isocyanurate (IRGANOX 3114).

The filler is present in one embodiment at 0.1-50% by weight, in another embodiment at 0.1-25% by weight of the composition, and in another embodiment at 0.2-10% by weight. Preferred fillers include but are not limited to titanium dioxide, silicon carbide, silica (and other oxides of precipitated or otherwise silica), antimony oxide, lead carbonate, zinc white, lithopone, zircon, corundum, spinel, apatite, barite, barium sulfate , Hydrotalcite compounds (with or without hydration) of magnesium, carbon black, dolomite, calcium carbonate, talc and ions Mg, Ca, or Zn with Al, Cr or Fe and CO ₃ and / or HPO ₄ ; Quartz powders, hydrochloric magnesium carbonates, glass fibers, clays, alumina and other metal oxides and carbonates, metal hydroxides, chromium, phosphorus and brominated flame retardants, antimony trioxide, silica, silicon and mixtures thereof. These fillers may in particular have any other fillers and porous fillers and supports known in the art, and in one embodiment may have the NFP of the present invention either precontacted or preabsorbed into the filler prior to addition to the polyolefin.

More specifically, in one embodiment of the invention, the NFP or a portion of the NFP may be mixed with a filler, preferably a porous filler. The NFP and filler may be mixed by, for example, a tumbler or other wet mixer. The NFP and filler are mixed in one embodiment for a suitable time to form a homogeneous composition of the NFP and filler, in one embodiment preferably for 1 minute to 5 hours. The NFP / filler mixture is then mixed with the polyolefins useful in the present invention to effect plasticization of the polyolefins. In another embodiment, the porous filler is contacted with NFP or a portion thereof before contacting the filler with the polyolefin. In another embodiment, the porous filler, polyolefin, and NFP are contacted simultaneously (or in the same mixing device). In any case, the NFP is present in the composition at 0.1-60% by weight, in another embodiment 0.2-40% by weight, and in still other embodiments 0.3-20% by weight.

Fatty acid salts may also be present in the polyolefin compositions of the invention. Such salts are present in amounts of 0.001 to 1% by weight in one embodiment and 0.01 to 0.8% by weight in another embodiment. Examples of fatty acid metal salts are lauric acid, stearic acid, succinic acid, stearyl lactic acid, lactic acid, phthalic acid, benzoic acid, hydroxystearic acid, ricinoleic acid, naphthenic acid, oleic acid, palmitic acid and erucic acid, suitable metals ( Li, Na, Mg, Ca, Sr, Ba, Zn, Cd, Al, Sn, Pb) and the like. Preferably the fatty acid salt is selected from magnesium stearate, calcium stearate, sodium stearate, zinc stearate, calcium oleate, zinc oleate and magnesium oleate.

The resulting plasticized polyolefins of the present invention may be any suitable means (e.g. calendering, casting, coating, compounding, extrusion, foaming, laminating, blow molding, compression molding, injection molding, thermoforming, transfer molding, By molding, rotomolding, for example casting for films, spinning or melt bonding for fibers, or by other forms for processing as disclosed, for example, in PLASTICS PROCESSING (Radian Corporation, Noyes Data Corp. 1986). Can be processed. More specifically, with regard to the physical process of preparing the mixture, sufficient mixing must take place so that a homogeneous mixture can be produced before conversion to the final product.

More specifically, the components of the polyolefin composition of the present invention may be mixed by any suitable method to form plasticized polyolefins suitable for further processing into useful products. In one embodiment of the invention, the polyolefin and NFP are mixed or melt mixed in an apparatus such as an extruder or a Brabender mixer. The polyolefin may also be mixed with the NFP using a tumbler, double cone mixer, ribbon mixer or other suitable mixer. In another embodiment, the polyolefin and NFP can be mixed, for example by a combination of tumblers followed by melt mixing in the extruder. Extrusion techniques for polypropylene are described in detail in PLASTICS EXTRUSION TECHNOLOGY 26-37 (Friedhelm Hensen, ed. Hanser Publishers 1988) and POLYPROPYLENE HANDBOOK 304-348 (Edward P. Moore, Jr. ed., Hanser Publishers 1996). .

More specifically, the components of the polyolefin composition of the present invention may be mixed in solution by any suitable method to form plasticized polyolefins using a solvent that dissolves all of the components to a significant extent. Such mixing may occur at any temperature or pressure at which NFP and polyolefin remain in solution. Preferred conditions include mixing at a temperature above 20 ° C., preferably above 40 ° C. above the melting point of the polyolefin. For example, iPP is generally a solution mixed with NFP at a temperature of at least 200 ° C, preferably at least 220 ° C. This solution mixing is particularly useful for processes in which polyolefins are prepared by solution processing and NFP is added directly to the finishing train without addition to the anhydrous polymer with other mixing steps. Such solution mixing will also be particularly useful in processes where polyolefins are prepared in bulk or high pressure processes where both polymer and NFP are soluble in monomers. Using the solution method, the NFP is added directly to the finishing train rather than to the anhydrous polymer along with the other mixing steps.

Polyolefins suitable for use in the present invention may exist in any physical form when used for mixing with the NFP of the present invention. In one embodiment, reactor granules defined as granules of polymer isolated from the polymerization reactor can be mixed with the NFP of the present invention. The reactor granules have an average diameter of 10 μm to 5 mm and in another embodiment have an average diameter of 50 μm to 10 mm. Optionally, the polyolefin is in the form of pellets having an average diameter of 1 to 6 mm, formed for example from melt extrusion of reactor granules.

One method of mixing NFP and polyolefin is to contact the components in a tumbler, where the polyolefin is in the form of reactor granules. This works particularly well with polypropylene homopolymers. Subsequently, the mixture is melt mixed in an extruder, as the case may be. Another way of mixing the components is to melt mix the polyolefin pellets directly with the NFP in an extruder or brabender.

Thus, in the case of injection molding of various products, simple solid state mixtures of pellets are pellets of crude polymer granules, or granules and pellets, or pellets of two components, since the molding process involves remelting and mixing of the crude material. Works as well as the fused molten mixture. However, in the process of compression molding of medical devices, the molten components do not mix well, and a pelletized molten mixture will be preferable to a simple solid state mixture of constituent pellets and / or granules. Those skilled in the art will be able to determine the appropriate procedure for the mixing of the polymer to balance the need for intimate mixing of the components with the need for process costs.

The polyolefin compositions of the present invention are suitable for casting and blowing automotive components, wire and cable jackets, pipes, agricultural films, geomembrane, toys, sports equipment, medical devices, packaging films, extrusion of pipes, pipes and profiles, sports It is suitable for products such as equipment, outdoor furniture (eg garden furniture) and playground facilities, boats and waterborne components and other products. In particular, the compositions include automotive components such as bumpers, grilles, trim parts, instrument panels and instrument panels, exterior door and hood components, spoilers, wind screens, wheel caps, mirror housings, body panels, protective side moldings, and automobiles, trucks. It is suitable for other interior and exterior components related to boats, boats and other vehicles.

Other useful products and goods can be economically formed by the practice of the present invention. That is, boxes, containers, packaging, laboratory equipment such as roller bottles and media bottles for medium growth, office floor mats, metrology sample holders and sample windows; Liquid storage containers such as bags, pouches and bottles for the storage and IV infusion of blood or solutions; Packaging materials, such as unit-dose or other blisters or bubble packs, including those for packaging or containing foods preserved by radiation, as well as for any medical device or drug. Other useful products are medical tubing and valves for any medical device, such as for infusion kits, catheters and respiratory therapies, medical devices, or packaging for radiated foods, including stocks or stocks, especially water, milk or juices. Materials, containers containing unit servings and bulk storage containers, as well as conveying means for piping, pipes and the like.

Such devices can be made or formed by any useful forming method for forming polyolefins. This includes at least molding, including compression molding, injection molding, blow molding, and transfer molding; Film blowing or casting; Extrusion and thermoforming; And lamination, drawing, protrusion, draw reduction, rotational molding, spin bonding, melt spinning, melt blowing; Or combinations thereof. At least thermoforming or film application applications allow the possibility of deriving advantages from uniaxial or biaxial orientation of the radiation resistant material.

In certain embodiments, the plasticized polyolefins prepared by the present invention may be mixed with one or more other polymers including, but not limited to, thermoplastic polymers and / or elastomers.

By "thermoplastic polymer" is meant a polymer that can be melted by heat and cooled without significant change in properties. Thermoplastic polymers generally include, but are not limited to, polyolefins, polyamides, polyesters, polycarbonates, polysulfones, polyacetals, polylactones, acrylonitrile-butadiene-styrene resins, polyphenylene oxides, polyphenylene sulfides , Styrene-acrylonitrile resin, styrene maleic anhydride, polyimide, aromatic polyketone or mixtures of two or more thereof. Preferred polyolefins include but are not limited to polymers comprising at least one linear, branched or cyclic C2 to C40 olefin, preferably at least one C3 to C40 olefin, preferably C3 to C20 alpha olefin, more preferably C3 to C10 alpha Polymers comprising propylene copolymerized with -olefins. More preferred polyolefins include, but are not limited to, polymers including, but not limited to, C3 to C40 olefins, preferably C3 to C20 alpha olefins, more preferably ethylene including but not limited to ethylene copolymerized with propylene and / or butene. .

"Elastomer" means all natural and synthetic rubbers, including those defined in ASTM D1566. Examples of preferred elastomers include, but are not limited to, ethylene propylene rubber, ethylene propylene diene monomer rubber, styrene block copolymer rubber (e.g., SI, SIS, SB, SBS, SIBS, etc., where S = styrene, I = Isobutylene, B = butadiene), butyl rubber, halobutyl rubber, copolymer of isobutylene and para-alkylstyrene, halogenated copolymer of isobutylene and para-alkylstyrene, natural rubber, polya Isoprene, copolymers of butadiene and acrylonitrile, polychloroprene, alkyl acrylate rubber, isoprene chloride chloride, acrylonitrile chloride isoprene rubber, polybutadiene rubber (both cis and trans) .

In another embodiment, the mixture comprising NFP comprises polybutene, ethylene vinyl acetate, low density polyethylene (density 0.915 to 0.935 g / cm ³ ), linear low density polyethylene, ultra low density polyethylene (density 0.86 to 0.90 g / cm ³ ), Very low density polyethylene (density 0.90 to 0.915 g / cm ³ ), medium density polyethylene (density 0.935 to 0.945 g / cm ³ ), high density polyethylene (density 0.945 to 0.98 g / cm ³ ), ethylene vinyl acetate, ethylene methyl acrylate , Copolymers of acrylic acid, polymethylmethacrylate or any other polymer polymerizable by the high pressure free radical method, polyvinylchloride, polybutene-1, isotactic polybutene, ABS resin, ethylene-propylene rubber (EPR), Vulcanized EPR, EPDM, Block Copolymer, Styrene Block Copolymer, Polyamide, Polycarbonate, PET Resin, Crosslinked Polyethylene, Ethylene And one or more of a copolymer of vinyl alcohol (EVOH), a polymer of aromatic monomers (e.g. polystyrene), poly-1 ester, polyacetal, polyvinylidene fluoride, polyethylene glycol and / or polyisobutylene May be further combined. Preferred polymers include those sold under the trade names EXCEED® and EXACT® from Exxon Chemical Company, Baytown, Texas.

The pressure sensitive adhesive may be mixed with a mixture of the polymer of the invention and / or the polymer produced by the invention (as described above). Examples of useful tackifiers include, but are not limited to, aliphatic hydrocarbon resins, aromatic modified aliphatic hydrocarbon resins, hydrogenated polycyclopentadiene resins, polycyclopentadiene resins, gum rosin, gum rosin esters, wood rosin, wood rosin esters, tall oil rosin , Tall oil rosin esters, polyterpenes, aromatic modified polyterpenes, terpene phenols, aromatic modified hydrogenated polycyclopentadiene resins, hydrogenated aliphatic resins, hydrogenated aliphatic aromatic resins, hydrogenated terpenes and modified terpenes, and hydrogenated rosin esters do. In some embodiments, the tackifier is hydrogenated. In other embodiments, the pressure sensitive adhesive is nonpolar (nonpolar means that the pressure sensitive adhesive contains substantially no monomers having polar groups. However, preferably the polar groups are at least 5% by weight, preferably at least 2% by weight, more preferably Preferably no polar group is present). In some embodiments, the tackifier has a softening point (ring and ball, measured by ASTM E-28) of 80 to 140 ° C., preferably 100 to 130 ° C. The tackifier, if present, is generally present at from about 1 to about 50 weight percent, more preferably from 10 to 40 weight percent, more preferably from 20 to 40 weight percent, based on the weight of the mixture. However, preferably the tackifier is absent or, if present, less than 10% by weight, preferably less than 5% by weight, preferably less than 1% by weight.

In another embodiment, the polymers of the present invention and / or mixtures thereof may include fillers, co-agents, antioxidants, surfactants, adjuvants, plasticizers, blocks, antiblocks, color masterbatches, pigments, dyes, processing aids, UV stabilizers. General additives known in the art such as, neutralizing agents, lubricants, waxes, and / or nucleating agents. These additives are generally present in amounts of 0.001 to 10% by weight, in effective amounts known in the art.

Preferred fillers, co-agents and / or nucleating agents include titanium dioxide, calcium carbonate, barium sulfate, silica, silicon dioxide, carbon black, sand, glass beads, inorganic aggregates, talc, clays and the like.

Preferred antioxidants include phenolic antioxidants such as Irganox 1010, Irganox 1076 (all available from Ciba-Geigy). Preferred oils include paraffinic or naphthenic oils such as Primol 352, or Primol 876, available from ExxonMobil Chemical France, S. A., Paris. More preferred oils include aliphatic naphthenic oils, white oils and the like.

Applications

The compositions of the present invention (and mixtures thereof as described above) can be used in any known thermoplastic or elastomeric application. For example, molded parts, films, tapes, sheets, piping, hoses, sheet metals, wire and cable coatings, adhesives, soles, bumpers, gaskets, corrugated pipes, films, fibers, elastic fibers, nonwovens, spunbonding, sealants, Applications in surgical gowns and medical devices.

glue

The polymers of the present invention or mixtures thereof may be used alone or in combination with an adhesive as an adhesive. Preferred adhesives have been described above. The tackifier is generally present in an amount of about 1 to about 50 weight percent, more preferably 10 to 40 weight percent, more preferably 20 to 40 weight percent, based on the total weight of the mixture. Other additives as described above may also be added.

The adhesives of the present invention can be used for any adhesive use including, but not limited to, disposables, packaging, laminates, pressure sensitive adhesives, tape labels, wood bonds, paper bonds, nonwovens, road markings, reflective coatings, and the like. In a preferred embodiment, the adhesives of the present invention can be used in disposable diaper and sanitary napkin body components, elastic adhesives in disposable product converting, packaging, labeling, bookbinding, woodworking and other assembly applications. Particularly preferred applications are infant diaper leg elastics, diaper frontal tapes, diaper upright leg cuffs, diaper body components, diaper core stabilizers, diaper liquid moving layers, diaper outer cover laminates, diaper elastic cuff laminates, sanitary napkin core stabilizers Packaging, sanitary napkin adhesive strip, industrial filtration bonding, industrial filter material lamination, filter mask lamination, surgical gown lamination, surgical drape lamination and easy-to-perish product packaging.

film

The compositions described above and mixtures thereof can be formed into single or multilayer films. These films can be formed by any conventional technique known in the art, including extrusion, coextrusion, extrusion coating, lamination, blowing and casting. The film may be obtained by a planar film or by a tubular process that is oriented in a uniaxial direction or two mutually perpendicular directions in the plane of the film. One or more film layers may be oriented in the transverse and / or longitudinal direction to the same or different degrees. This orientation occurs before or after the individual layers are brought together. For example, the polyethylene layer is extrusion coated or laminated onto an oriented polypropylene layer, or the polyethylene and polypropylene are oriented after coextrusion together into a film. Likewise, the oriented polypropylene may be laminated to the oriented polyethylene or the oriented polyethylene may be coated onto the polypropylene and optionally the combination may then be further oriented. Generally the films are oriented in the Machine Direction (MD) at a ratio of 15 or less, preferably 5 to 7, and in the Transverse Direction (TD) at a ratio of 15 or less, preferably 7 to 9. However, in another embodiment the film is oriented to the same extent in both the MD and TD directions.

In another embodiment, the layer comprising the plasticized polyolefin composition (and / or mixtures thereof) of the present invention may be combined with one or more other layers. The other layer can be any layer generally included in a multilayer film structure. For example, the other layer (s) are as follows:

1. Polyolefin

Preferred polyolefins are homopolymers or copolymers of C2 to C40 olefins, preferably C2 to C20 olefins, preferably alpha olefins and copolymers of other olefins or alpha-olefins (ethylene is defined as alpha olefins for the purposes of the present invention). It is included). Preferably ethylene copolymerized with at least one of propylene, propylene, butene or hexene and optional dienes copolymerized with homopolyethylene, homopolypropylene, ethylene and / or butene. Preferred examples are ultra low density polyethylene, very low density polyethylene, linear low density polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, propylene and ethylene And / or random copolymers of butene and / or hexene, elastomers such as ethylene propylene rubber, ethylene propylene diene monomer rubber, neoprene, and mixtures of thermoplastic polymers and elastomers such as thermoplastic elastomers and rubber toughened Thermoplastic polymers such as plastics.

2. Polar polymer

Preferred polar polymers are homopolymers and copolymers of esters, amides, acetates, anhydrides, copolymers of C2 to C20 olefins, for example one or more polar monomers (eg acetate, anhydrides, esters, alcohols, and / or acrylics). ) Is a copolymer of ethylene and / or propylene and / or butene. Preferred examples include polyesters, polyamides, ethylene vinyl acetate copolymers and polyvinyl chlorides.

3. Cationic Polymer

Preferred cationic polymers include polymers and copolymers of co-substituted olefins, alpha-heteroatomic olefins and / or styrene monomers. Preferred co-substituted olefins include isobutylene, isopentene, isoheptene, isohexane, isooctene, isodedecene, and isododecene. Preferred alpha-heteroatom olefins include vinyl ether and vinyl carbazole, and preferred styrene monomers are styrene, alkyl styrene, para-alkyl styrene, alpha-methyl styrene, chloro-styrene, and bromo- Para-methyl styrene. Preferred examples of the cationic polymer include butyl rubber, isobutylene, polystyrene and poly-alpha-methyl styrene copolymerized with para methyl styrene.

4. Other

Other preferred layers include paper, wood, cardboard, metal, metal foils (such as aluminum foil and tin foil), metallized surfaces, glass (silicon oxide (SiOx)) onto the film surface and applied silicon oxide coatings applied. ), Fabrics, spunbonded fibers and nonwovens (particularly polypropylene spunbonded fibers or nonwovens), and substrates coated with inks, dyes, pigments, and the like.

The film may vary in thickness depending on the intended use, but a film thickness of 1 to 250 μm is appropriate. Films intended for packaging are typically 10 to 60 microns thick. The thickness of the sealing layer is generally 0.2 to 50 mu m. A sealing layer may be present on both the inner and outer surfaces of the film or the sealing layer may be present only on the inner surface or only on the outer surface.

Additives such as blocks, antiblocks, antioxidants, pigments, fillers, processing aids, UV stabilizers, neutralizing agents, lubricants, surfactants and / or nucleating agents may be present in one or more layers of the film. Preferred additives include silicon dioxide, titanium dioxide, polydimethylsiloxane, talc, dyes, waxes, calcium stearate, carbon black, low molecular weight resins and glass beads.

In one embodiment, one or more layers can be modified by corona treatment, electron beam radiation, gamma radiation, or microwave radiation. In a preferred embodiment one or both of the surface layers are modified by corona treatment.

The films described herein comprise between 5 and 60% by weight hydrocarbon resin, based on the weight of polymer and resin. Such resins may be combined with the polymer of the sealing layer or with the polymer in the core layer. The resin preferably has a softening point of 100 ° C. or higher, more preferably 130 to 180 ° C. Preferred hydrocarbon resins include those described above. Films comprising hydrocarbon resins can be oriented in the uniaxial or biaxial directions to the same or different degrees.

The film described above can be used as a stretchable and / or tacky film. Stretch / adhesive films can be used for a variety of bundling, packaging and cargo handling operations. Many known adhesive additives have been used to impart tack to certain films or to improve their tack. Typical tackifier additives include polybutenes, terpene resins, alkali metal stearates and hydrogenated rosin and rosin esters. The tack of the film can also be modified by well known physical methods such as corona discharge. Some polymers (eg ethylene methyl acrylate copolymers) do not require adhesive additives and can be used as adhesive layers without additives. The stretch / tacky film can be any suitable polyolefin or combination of polyolefins (e.g. polyethylene, polypropylene, copolymers of ethylene and propylene, and polymers obtained from ethylene and / or propylene copolymerized with other olefins, especially C4 to C12 olefins) It may include a slip layer comprising a. Especially preferred are polypropylene and linear low density polyethylene (LLDPE). Suitable polypropylenes are typically solid and isotactic, ie, high temperature heptane insoluble materials having a wide melt flow rate of about 0.1 to about 300 g / 10 min. Additionally, the slip layer may include one or more anti-stick (slip and / or antiblock) additives that may be added during the preparation of the polyolefin or subsequently mixed therein to enhance the slip properties of such layer. have. Such additives are well known in the art and include, for example, silica, silicates, diatomaceous earth, talc and various lubricants. These additives are preferably used in amounts of about 100 to about 20,000 ppm, more preferably about 500 to about 10,000 ppm, based on the weight of the slip layer.

In some cases, the slip layer also includes one or more additives as described above.

Molded product

The plasticized polyolefin compositions described above also include, but are not limited to, injection molding, gas assisted injection molding, extrusion blow molding, injection blow molding, injection stretch blow molding, compression molding, rotational molding, foam molding, thermoforming, sheet extrusion and profiles. Any molding method, including extrusion, can be used to make the molded article of the present invention. Molding methods are well known to those skilled in the art.

The compositions described herein may be shaped into the desired end use product by any suitable means known in the art. Thermoforming, Vacuum Forming, Blow Molding, Rotational Molding, Slush Molding, Transfer Molding, Wet Lay-up or Contact Molding, Casting Molding, Cold Forming Matched-die Molding , Injection molding, spray technology, profile coextrusion, or a combination thereof is a commonly used method.

Thermoforming is the process of forming one or more flexible plastic sheets into an intended shape. One embodiment of the thermoforming sequence is described, but this should not be construed as limiting the thermoforming method for use with the compositions of the present invention. First, a compact film (and any other layer or material) of the composition of the present invention is placed on a shuttle rack and kept under heating. The shuttle rack is indexed on an oven and the film is preheated prior to molding with the oven. Once the film is heated, the shuttle rack is indexed back to the forming tool. The film is then evacuated onto the forming tool to hold it in place and close the forming tool. The forming tool may be a "convex" or "concave" shaped tool. Leave the tool closed, cool the film, and open the tool. The shaped stack is removed from the tool.

Thermoforming is performed by vacuum, positive air pressure, plug-assisted vacuum forming, or combinations and modifications thereof once the material sheet has reached a thermoforming temperature, typically 140 ° C. to 185 ° C. or higher. In order to improve material distribution, a pre-stretched bubble step is used, especially on large portions. In one embodiment, the articulating rack lifts the heated stack towards the convex forming tool, which is assisted by vacuum application from the orifice in the convex forming tool. Once the stack is firmly formed around the convex forming tool, the thermoformed shaped stack is generally cooled by a blower. Plug-assisted molding is generally used for small deep drawn parts. Plug material, design and timing are important for the optimization of these processes. Plugs made from insulating foams avoid premature quenching of the plastic. The plug shape is typically similar to the mold cavity but without the smaller and more detailed parts. Round plug bottoms typically promote uniform material distribution and uniform sidewall thickness. For semicrystalline polymers such as polypropylene, fast plug speeds generally result in the best material distribution in that portion.

The shaped stack is cooled in the mold. Sufficient cooling is preferred to maintain the mold temperature at 30 to 65 ° C. This portion is below 90-100 ° C. prior to discharge in one embodiment. For good behavior in thermoforming, the lowest melt flow rate polymer is preferred. The shaped stack is edged with excess stack material.

Blow molding is another suitable molding method, which includes injection blow molding, multilayer blow molding, extrusion blow molding and stretch blow molding, and is particularly suitable for substantially closed or hollow objects, such as gas tanks and other fluid containers. Do. Blow molding is described in more detail in CONCISE ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING 90-92 (Jacqueline I. Kroschwitz, ed., John Wiley & Sons 1990).

In another embodiment of the molding and shaping process, profile coextrusion may be used. The profile coextrusion process parameters are as described above for the blow molding method, except that the die temperature (double zone top and bottom) is 150 to 235 ° C, the supply block is 90 to 250 ° C and the water cooling bath temperature is 10 to 40 ℃.

One embodiment of the injection molding method is described as follows. The shaped stack is placed in an injection molding tool. The mold is closed and the substrate material is injected into the mold. The substrate material is, in one embodiment, a melting point of 200-300 ° C., 215-250 ° C. and pushed into the mold at an injection rate of 2-10 seconds. After injection, the material is packed and held at a predetermined time and pressure to make the molded article dimensionally aesthetically accurate. Typical time zones are 5 to 25 seconds and pressures are 1,380 kPa to 10,400 kPa. The mold is cooled to 10-70 ° C. to cool the substrate. The temperature depends on the intended gloss and appearance requirements. Typical cooling times are 10 to 30 seconds depending on the thickness of the part. Finally, the mold is opened and the shaped composite product is discharged.

Molded articles are likewise produced by injecting molten polymer into a mold, which molds and solidifies the molten polymer to the desired geometry and thickness of the molded article. The sheet may be made by extruding a substantially planar profile from the die, onto a chill roll, or optionally by calendaring. The sheet is generally considered to have a thickness of 10 to 100 mils (254 to 2540 μm), but may be substantially thicker. Tubing or pipes can be obtained by profile extrusion for use in medical, beverage, sewage device applications and the like. This profile extrusion method involves extruding molten polymer through a die. The extruded tubing or pipe is solidified by cooling water or by cooling the air onto a continuously extruded product. Tubing generally has an outside diameter of 0.31 cm to 2.54 cm and a wall thickness of 254 μm to 0.5 cm. Pipes generally have an outside diameter of 2.54 cm to 254 cm and a wall thickness of 0.5 cm to 15 cm. Sheets made from the product of one embodiment of this invention can be used to form containers. Such containers can be formed by thermoforming, solid phase pressure forming, stamping and other shaping techniques. The sheet may also be shaped to cover the floor or wall or other surface.

In one embodiment of the thermoforming method, the oven temperature is 160-195 ° C., the time in the oven is 10-20 seconds, and the die temperature, generally convex die, is 10-71 ° C. The final thickness of the cooled (room temperature) shaped laminate is 10 to 6000 μm in one embodiment, 200 to 6000 μm in another embodiment, 250 to 3000 μm in another embodiment and 500 in another embodiment. 1550 micrometers, and a preferable range is arbitrary combinations of arbitrary upper limit and lower limit.

In one embodiment of the injection molding method in which the substrate material is molded into a tool comprising a shaped laminate upon injection, the melting point of the substrate material is 230-255 ° C. in one embodiment and 235-250 ° C. in another embodiment. , Charging time is 2 to 10 seconds in one embodiment, 2 to 8 seconds in another embodiment, and tool temperature is 25 to 65 ° C. in one embodiment and 27 to 60 ° C. in another embodiment. In a preferred embodiment, the temperature of the substrate material is a temperature hot enough to melt any bonding layer material or backing layer to achieve interlayer adhesion.

In another embodiment of the present invention, the composition of the present invention may be secured to the substrate material using a blow molding operation. Blow molding is particularly useful for such applications for manufacturing closed products such as fuel tanks and other fluid containers, playground facilities, outdoor furniture and small packaging structures. In one embodiment of this process, the composition of the present invention is extruded through a multilayer head and the uncooled laminate is placed into a Parison in the mold. The mold is closed, whether convex or concave in its interior, and blows air into the mold to form a molded article.

Those skilled in the art will understand that the steps outlined above may vary depending on the intended results. For example, the extruded sheet of the composition of the present invention can be directly thermoformed or blow molded without cooling, thus omitting the cooling step. Other factors can also be varied to obtain a final composite product of the desired properties.

Nonwovens and Textiles

The plasticized polyolefin compositions described above may also be used to make the nonwoven fabrics and fibers of the present invention with any nonwoven fabric and fiber manufacturing process, including but not limited to melt blown, spunbond, film perforated, and staple fiber carding. Can be. Continuous filament processes are also used. Preferably a spunbonding process is used. Such spunbonding processes are well known in the art. It is generally associated with the extrusion of fibers through the spinneret. These fibers are drawn using high velocity air and placed on endless belts. Calender rolls are generally used to heat the web and bond the fibers together, although other techniques such as sonic bonding and adhesive bonding may be used. The fabric may be made with mixed metallocene polypropylene alone, physically mixed with other mixed metallocene polypropylene or physically mixed with a single metallocene polypropylene. The fabrics of the invention can likewise be made using mixed metallocene polypropylene physically mixed with conventional Ziegler-Natta produced polymers. Once mixed, the fabric of the present invention is preferably composed of at least 50% mixed metallocene polypropylene. With these nonwoven fabrics, manufacturers can maintain the desirable properties of fabrics made using metallocene produced polypropylene while increasing fabric strength and thus provisionally line speed compared to fabrics made using conventional polymers. Increased.

Test Methods

Synchronous thermal analysis

Glass transition temperature (Tg) and storage modulus (E ') were measured using synchronous thermal analysis (DMTA). This test provides information on the small strain mechanical response (relaxation behavior) of the sample as a function of temperature over a temperature range including the glass transition region and the viscoelastic region before melting.

In general, samples are measured using a three point flexure structure (TA Instruments DMA 2980). A solid rectangular compression molded bar is placed on two fixed support plates; The movable clamp applied periodic strain at the midpoint of the sample with a frequency of 1 Hz and an amplitude of 20 μm. The sample was initially cooled to −130 ° C. and heated to 60 ° C. at a heating rate of 3 ° C./min. In some cases, compression molded bars were tested using different strain configurations, ie double cantilever bending and tensile elongation (Rheometrics RSAII). Under these arrangements, periodic strain was applied at a frequency of 1 Hz and strain amplitude of 0.05%. The sample was cooled to −130 ° C. and heated to 60 ° C. at a heating rate of 2 ° C./min. Minor differences in heating rate have little effect on glass transition temperature measurements.

The outputs of the DMTA experiment are the storage modulus (E ') and the loss modulus (E "). The storage modulus is a measure of the elastic response or energy storage of the material, and the loss modulus is the dissipation of the Tan δ is the E ″ / E ′ ratio and provides a measure of the braking ability of the material. The onset of broad glass transition (β-releasing) is identified as extrapolated tangent to the Tan δ peak. In addition, the peak temperature and the area under the peak are also measured to further characterize the transition from glassy to viscoelastic regions.

Differential Scanning Calorimeter

Crystallization temperature (Tc) and melting point (Tm) are measured by differential scanning calorimetry (DSC). This analysis is performed using TA Instruments MDSC 2920 or Perkin Elmer DSC7. In general, 6-10 mg of the molded or plasticized polymer is sealed in an aluminum pan and loaded on the instrument at room temperature. Melt data (first row) was obtained by heating the sample to at least 30 ° C. above the melting point at a heating rate of 10 ° C./min. This provides information about the melt behavior under molded conditions affected by thermal history, as well as any molded-in orientation or stress. The sample was held at this temperature for 10 minutes to break its thermal history. Crystallization data was obtained by cooling the sample from the melt to at least 50 ° C. below the crystallization temperature at a cooling rate of 10 ° C./min. The sample was held at 25 ° C. for 10 minutes and finally heated at 10 ° C./min to obtain additional melt data (second row). This provides information on melt behavior that is free from potential mold-in orientation and stress effects after controlled thermal history. Endothermic melt transitions (first and second rows) and exothermic crystallization transitions were analyzed for transition and onset of peak temperature. The melting point reported in the table is the peak melting point from the second column unless otherwise indicated. For polymers exhibiting multiple peaks, higher melt peak temperatures are recorded.

The area under the curve was used to determine the heat of fusion (ΔHf) that could be used to calculate the crystallinity. A value of 207 J / g was used as the equilibrium heat of fusion for 100% crystalline polypropylene (obtained from B. Wunderlich, "Thermal Analysis", Academic Press, Page 418, 1990). The crystallinity percentage is calculated using Equation 3 below.

[Area under the curve (J / g) / 207 (J / g)] * 100

Size-Exclusion Chromatography of Polymers

Molecular weight distribution was characterized using size-exclusion chromatography (SEC). Molecular weights (weight-average molecular weight (Mw) and number average molecular weight (Mn)) are determined by the High Temperature Size Exclusion Chromatograph (Digital Chromatograph) equipped with a differential refractive index detector (DRI), an online light dispersion detector and a viscometer. From Waters Corporation) or Polymer Laboratories. Details of the experiments not described below, such as how to test the detector, are described in T. Sun, P. Brant, R. R. Chance, and W. W. Graessley, Macromolecules, Volume 34, Number 19, 6812-6820, (2001).

Three Polymer Laboratories PLgel 10 mm Mixed-B columns were used. The nominal flow rate was 0.5 cm ³ / min and the nominal injection volume was 300 μl. Various transfer lines, columns and differential refractometers (DRI detectors) were placed in an oven maintained at 130 ° C.

Solvents for SEC experiments were prepared by dissolving 6 g of butylated hydroxy toluene as antioxidant in 4 L of Aldrich's reagent grade 1,2,4 trichlorobenzene (TCB). The TCB mixture was filtered through a 0.7 μm glass pre-filter and subsequently through a 0.1 μm Teflon filter. The TCB was degassed with an online degasser before entering the SEC.

The polymer solution was prepared by placing anhydrous polymer in a glass container, adding the desired amount of TCB and heating the mixture at 160 ° C. for about 2 hours with continuous stirring. All amounts were measured by weight. The TCB density used to express the polymer concentration in mass / volume units was 1.463 g / ml at room temperature and 1.324 g / ml at 135 ° C. Injection concentrations range from 1.0 to 2.0 mg / ml and lower concentrations can be used for higher molecular weight samples.

Prior to performing each sample, the DRI detector and syringe were purged. The flow rate in the device increased to 0.5 ml / min and the DRI stabilized for 8 to 9 hours before injecting the first sample. The LS laser was turned on 1 to 1.5 hours before performing the sample.

The concentration (c) at each point in the chromatogram was calculated from the baseline minus DRI signal, I _DRI using Equation 4:

c = K _DRI I _DRI / (dn / dc)

Where

K _DRI is a constant measured by testing the DRI, and (dn / dc) is the same as described below for LS analysis.

The unit of factors through this technique of the SEC method is that the concentration is expressed in g / cm ³ , the molecular weight in g / mol, and the intrinsic viscosity in dL / g.

The light scattering detector used was the Watt Technology High Temperature mini-DAWN. The polymer molecular weight (M) at each point in the chromatogram was determined by analyzing the LS output using a Zimmm model for static light scattering (MB Huglin, LIGHT SCATTERING FROM POLYMER SOLUTIONS, Academic Press, 1971). ]:

Where

ΔR (θ) is the excess Rayleigh scattering intensity measured at scattering angle θ, c is the polymer concentration measured from the DRI analysis, A ₂ is the second Viral coefficient, and P (θ) is monodispersion Is a formation factor for the random coil (described in the references above), and K _o is an optical constant according to equation (6) for the system.

Where

N _A is the Avogadro's number and (dn / dc) is the refractive index increment for the system. The refractive index n is 1.500 for the TCB at 135 ° C. and λ = 690 nm. Also, A ₂ for propylene polymer is 0.0006, 0.0015 for butene polymer, (dn / dc) is 0.104 for propylene polymer and 0.098 for butene polymer.

A high temperature Viscotek Corporation viscometer is used, which has four capillaries with two pressure transducers arranged in a Wheatstone bridge configuration. One transducer measures the total pressure drop across the detector and the other measures between the two sides of the bridge to measure different differential pressures. The specific viscosity η _s for the solution flowing through the viscometer is calculated from their output. The intrinsic viscosity [η] at each point in the chromatogram is calculated from Equation 7:

η _s = c [η] + 0.3 (c [η]) ²

Where

c was measured from the DRI output.

The branching index (g ') is calculated using the output of the SEC-DRI-LS-VIS method as follows. The average intrinsic viscosity [η] _avg of the sample is calculated by the following equation.

Where

The sum is over the chromatograph fragment i between the integration limits.

The branching index g 'is defined as

Where

K = 0.0002288 for the propylene polymer and α = 0.705, k = 0.00018 for the butene polymer and α = 0.7. Mv is the viscosity average molecular weight based on the molecular weight measured by LS analysis.

¹³ C-NMR spectroscopy

The polymer microstructure containing the isotactic and syndiotactic diad ([m] and [r]), triad ([mm] and [rr]), and pentads ([mmmm] and [rrrr]) ¹³ It was examined by C-NMR spectroscopy. The sample was dissolved in d ₂ -1,1,2,2-tetrachloroethane. Spectra were recorded at 125 ° C. using an NMR spectrometer at 75-100 MHz. Polymer resonance peaks were referenced to mmmm = 21.8 ppm. Calculations relating to the characterization of polymers by NMR are described in FA Bovey, "Polymer Conformation and Configuration" Academic Press, New York 1969 and J. Randall, "Polymer Sequence Determination, ¹³ C-NMR Method", Academic Press, New York, 1977]. The percentage% (CH ₂ ) 2 of the methylene sequence of length ₂ was calculated as follows: an integral of 14 to 18 ppm of methyl carbon (equal to the concentration for the number of methylene sequences of 2 in length) of 45 to Divide by the integral of the methylene sequence of length 1 between 49 ppm and the integral of methyl carbon of 14-18 ppm and multiply by 100. This is the minimum calculated for the amount of methylene groups contained in two or more sequences since methylene sequences greater than two were excluded. The study is described in HN Cheng and JA Ewen, Makromol. Chem. 1989, 190, 1931].

Viscosity of Polymers and Mixtures

Shear viscosity as a function of shear rate was measured using a double-barrel capillary flow meter. The capillary flow meter (Rosand Model RAH7 / 2, Bohun Instruments) was equipped with a 30: 1 length to diameter ratio capillary. A total of 25-30 g of pellet mass is packed in a capillary barrel and preheated at 230 ° C. for 10 minutes to remove any entrained air before testing. Each test was performed at 230 ° C. over a shear rate range of 30 to 3000 s ⁻¹ . Data correction for inlet pressure loss (ie, Bagley correction) was performed online by measuring simultaneous pressure loss for the flow of material through the orifice mounted into the second barrel of the flow meter.

Dynamic shear viscosity as a function of frequency was measured by small amplitude vibration shear rheology. A Rheometrics Scientific DSR-500 dynamic stress-controlled rheometer with conical plate sample mounting was used. The test was performed at 190 ° C. The sample was vibrated at a fixed frequency with the upper cone oscillated at a vibration shear stress at a nominal amplitude of 100 Pa and the resulting strain was measured. The strain was maintained within 1-30% using auto-stress adjustment (stress control setting = 32% of current stress, maximum stress = 100 Pa). Under these conditions, each material can be reliably characterized within the linear viscoelastic region. Dynamic shear viscosity was calculated as a function of frequency from measured strain and applied stress. Frequency sweep was performed starting at 500 rad / s and decreasing to 0.02 rad / s using the logarithmic sweep mode with 6 points per 10 units.

The kinematic viscosity (η ^* ) versus frequency (ω) curves were created using a cross model (as described in CW Macoskco, "Rheology: Principles, Measurements, and Applications", Wiley-VCH, 1994). ]:

The three factors in this model are the zero-shear viscosity (η ₀ ), the mean relaxation time (λ), and the square index (n). The zero-shear viscosity is a value in the flat region in the Newtonian region of the flow curve at low frequencies, where the kinematic viscosity is independent of the frequency. The mean relaxation time corresponds to the inverse of the frequency at which shear-thinning is initiated. The square index n is the slope of the shear dining area at high shear velocity in the log-log plot of the kinematic viscosity. These factors provide a means for comparing the effect of plasticization on the flow behavior of materials, sensitivity to shear and molecular structure.

Melt Flow Rate of Polymers and Mixtures

Melt flow rate (MFR) is measured according to ASTM D1238 at 230 ° C. under a load of 2.16 kg. Melt index (MI) is measured according to ASTM D1238 at 190 ° C. under a load of 2.16 kg. The unit is g / 10 min, or dg / min.

Polymer density

 Density is measured by density-gradient columns on compression-molded test pieces that are slowly cooled to room temperature, as disclosed in ASTM D1505.

Mechanical properties

Specimens for testing mechanical properties were injection molded unless otherwise indicated. Test temperatures are standard laboratory temperatures (23 ± 2 ° C.) unless otherwise indicated, as specified in ASTM D618. Instron loading frames were used for tensile and flexural testing.

Young's modulus (also called elastic modulus), yield stress (also referred to as tensile strength at yield), yield strain (also called elongation at yield), fracture stress (also referred to as tensile strength at break), and Tensile properties, including fracture strain (also called elongation at break), were measured according to ASTM D638. Yield energy is defined as the area under the stress-strain curve from zero strain to yield strain. Fracture energy is defined as the area under the stress-strain curve from zero strain to fracture strain. Injection molded tensile bars have ASTM D638 Type I or Type IV geometry when tested at a rate of 2 in / min. The compression molded tension bars have an ASTM D412 Type C geometry when tested at a speed of 20 inch / min. For compression molded specimens only, the yield stress and yield strain were recorded as 10% offset values as defined in ASTM D638. Fracture properties were recorded only when most of the specimens failed before deformation of about 2000%, which is the maximum possible strain on the loading frame used for testing.

Flexural properties including 1% secant modulus and 2% secant modulus were measured according to ASTM D790A. The test piece geometry was embodied under "molding material (thermoplastic and thermoset)" and the support span was 2 inches.

Heat distortion temperature was measured at 66 psi on injection molded specimens in accordance with ASTM D648.

Rockwell hardness was measured using R-scale in accordance with ASTM D785.

Impact properties

Gardner impact strength was measured on a 0.125 in thick injection molded disc at a predetermined temperature in accordance with ASTM D5420.

Notched izod impact resistance was measured at a predetermined temperature in accordance with ASTM D256. A TMI Izod impact Tester was used. Test specimens were prepared by individually cutting from the center of an injection molded ASTM D638 Type I tension bar, or by cutting the pair of test specimens in half by injection molded ASTM D790 “molding material (thermoplastic and thermoset)” bars. The notches were oriented so that most of the impact occurred on the side that notched the specimen (following procedure A of ASTM D256). Notched orientation was reversed where specified (following procedure E of ASTM D256). All specimens were assigned a thickness of 0.122 in for the calculation of impact resistance. All destruction was complete unless otherwise indicated.

Optical properties

Haze was measured by ASTM D1003 on a 0.04 inch thick injection molded plate. Glossiness was measured according to ASTM D2457 at an angle of 45 °.

Fabric and Film Properties

Flexural and tensile properties (including 1% secant flexural modulus, peak loading, tensile strength at break and elongation at break) were measured by ASTM D 882. Elmendorf tears were measured according to ASTM D 1922. Perforation and puncture energy were measured according to ASTM D 3420. Total energy dart impact was measured by ASTM D 4272.

Soft or "hand" of spunbonded nonwoven fabrics as known in the art can be obtained using a Swing-Albert Handle-O-Meter (Model 211-10-B / America). Measured. The quality of the "hand" is considered a combination of resistance due to the surface friction and flexibility of the fabric material. The handle-o-meter measures the above two factors using a Linear Variable Differential Transformer (LVDT) to detect the resistance encountered by the wing when forcing a specimen of material into a slot on the parallel edge. A 3 1/2 numeric digital voltmeter (DVM) displays the resistance directly in g. The "total hand" of any given material sheet is the average of four readings taken on both sides and in both directions of the test sample and is reported in grams per standard butterfly of sample material. The decrease in "total hand" indicates an improvement in fabric ductility.

Fluid properties

Pour point is measured by ASTM D 97. Kinematic Viscosity (KV) is measured according to ASTM D 445. Specific gravity is generally measured by ASTM D 4052 at a given temperature. Viscosity index (VI) is measured by ASTM D 2270. Boiling point and distillation range are generally measured by ASTM D 86 or ASTM D 1160. Saturates and aromatic content are measured by various methods, for example ASTM D 3238.

The number average molecular weight (Mn) is measured by gas chromatography (GC) as described in "Modern Practice of Gas Chromatography", RL Grob and EF Barry, Wiley-Interscience, 3rd Edition (July 1995), Measured by gel permeation chromatography (GPC) or described in ASTM D 2502 as described in "Modern Size Exclusion Liquid Chromatographs", WW Yan, JJ Kirkland, and DD Bly, J. Wiley & Sons (1979). Or by freezing point drop as disclosed in "Lange's Handbook of Chemistry", 15th Edition, McGrawHill. The average carbon number (Cn) is calculated from Mn by Cn = (Mn-2) / 14.

Processing method

mix

The components of the present invention may be mixed by any suitable method. For example, it may be mixed in a static mixer, a batch mixer, an extruder, or a combination thereof, which is sufficient to achieve proper dispersion of the plasticizer in the polymer. The mixing step includes, for example, a first anhydrous mixing using a tumbler blender. Dispersion may occur in the extruder, for example on injection molding marching or fiber lines, as part of the processing method used to produce the product. Plasticizers can be injected onto the extruder barrel or introduced into the feed throat of the extruder to save premixing steps. This is the preferred method when using a large percentage of plasticizers.

Two general methods are used to prepare examples of plasticized mixtures. The first method is called the extruder method, and the reactor granules of the polymer are first "anhydrous mixed" in a tumble blender with an appropriate amount of plasticizer and additive package (including components such as antioxidants and nucleating agents) to produce the desired plasticizer and additive concentration. To achieve homogeneous mixing of the components. The mixture is then compounded and pelletized using an extruder (30 or 57 mm twin screw extruder) at a suitable extrusion temperature above the melting point of the polymer, but always in the range from 200 to 230 ° C. In some cases, samples of the desired plasticizer concentration were prepared by adding pure polymer pellets to the premixed plasticized polymer pellets at high plasticizer concentrations.

The second method, referred to as the Brabender method, involves mixing the polymer pellets with a plasticizer in a heated Seedable Oil Brabender Instruments Plasticorder to achieve a homogeneous melt at the desired plasticizer concentration. The Brabender is equipped with a Prep-Mixer head (about 200 cm ³ volume) and a roll blade. The operating temperature is above the melting point of the polymer but is always in the range of 180 to 190 ° C. The polymer is first melted at 60 RPM for 1 minute in a brabender. The plasticizer is added slowly to prevent pooling in the molten polymer. The mixture was then mixed for 5 minutes at 60 RPM under nitrogen purge. The brabender is opened and the melt is taken out of the mixing head and blade as soon as possible and left to solidify. To later introduce this mixture into injection molding, a piece of material from the brabender was cut into smaller pieces using a cutter and crushed into even smaller pieces using a Wiley Mill.

Injection molding

For materials mixed using the extruder method, standard ASTM tensile and HDT bars and Gardner impact discs were molded using a 120-ton injection molding apparatus in accordance with ASTM D4101. For materials mixed using the Brabender method, tensile and flex bars were molded using a 20 ton injection molding apparatus according to ASTM D4101, except for the following clues: the molding temperature was 40 ° C; Injection time was 30 seconds; Tensile and flex bars have ASTM D638 Type IV and ASTM D790 geometries, respectively; The melting point is optionally 10 ° C. from the ASTM D4101-specificized value but is always 190 to 200 ° C. (except for polybutene mixtures molded to melting points in the range of 220 to 230 ° C.).

Compression molding

The material to be molded was placed in a Carver press at 160 ° C. between two sheets of PTFE-coated aluminum foil on a 0.125 inch thick chase. The material was allowed to melt for 5 minutes without applying pressure and then compressed for 5 minutes at 10 tons pressure. It was then taken out and immediately placed between water-cooled cold platens and compressed at 10 tonne pressure for another 5 minutes. The foil-sample-foil assembly was annealed for at least 40 hours at room temperature and quenched in dry ice before removing the sample from the foil to prevent deformation of the material when peeling off the foil. Tensile and flexural specimens were removed from the mold out of the sample once warmed to room temperature.

Spunbonding Fabric Method

Typical spunbonding processes consist of continuous filament extrusion, drawing, web formation using some types of ejectors, and web bonding. The polymer pellets are once fed to the extruder. In the extruder, the pellets are melted simultaneously by a hot melt screw and pass through the system. At the end of the screw, the spin pump meters the molten polymer through the filter into the spinneret, where the molten polymer is extruded under pressure through the capillary at a rate of 0.4 g / hole / min. The spinneret has several hundred capillaries measuring 0.4 mm in diameter. The polymer melts at about 30-50 ° C. or more above its melting point to achieve a sufficiently low melt viscosity for extrusion. The fibers exiting the spinneret are quenched and drawn into fine fibers measuring about 16 μm diameter. The solidifying fibers are randomly placed on a moving belt to form a random mesh structure known as the web in the art. 25 basis weights (g / m 2) of the web are obtained by adjusting the belt movement speed. After the web is formed, the web is joined using a heated textile calendar known in the art as a thermally bonded calendar to achieve final strength. The calendar consists of two heated steel rolls, one roll is nothing and the other roll has a melting point pattern. The web is transported to a calender where the web is pressed between rolls at a bonding temperature of about 138 ° C. to form a fabric.

Casting film method

The cast film was produced using the following operation. Cast monolayer films were prepared on a Killion cast film line. This line had three 24: 1 L / D 2.54 cm diameter extruders, which feed the polymer to the feedblock. The feedblock converts the molten polymer from the extruder into a 20.32 cm wide Cloeren die. The molten polymer exits the die at a temperature of 230 ° C. and is cast on a cold roll (20.3 cm diameter, 25.4 cm roll surface) at 21 ° C. The casting apparatus has an adjustable winding speed to obtain a film of the desired thickness.

Determination of NFP Content in Mixtures

Method 1: Extract

One method for determining the amount of NFP in the mixture is Soxhlet extraction, where at least most of the NFP is extracted using reflux n-heptane. Analysis of the base polymer is also required because the base polymer contains low molecular weight and / or amorphous materials that are soluble in reflux n-heptane. The amount of plasticizer in the mixture is determined by correcting its extractable amount (% by weight) by the extractable amount relative to the base polymer as described below.

The saxlet extraction device comprises a 400 ml saxlet extractor, an expanded overflow tube (to prevent siphoning and provide constant flow extraction), a metal screen cage fixed in the main soxlet chamber; It consists of a one-neck 1000 ml round bottom flask with a saxlet extraction tumble (Whatman, single thickness, cellulose), a coolant and a drain with a drain and an appropriately sized stirrer and heating mantle located within the screen cage.

The procedure is as follows. The saxlet dumble is dried in a 95 ° C. oven for about 60 minutes. The dry dimples are weighed immediately after taking them out of the oven and the weight is recorded as A: gross weight of the previous dumble. 15-20 g of sample (in the form of pellets or ground pellets) are weighed into the dumble. This is reported as B: polymer weight in grams. The tumble containing the polymer is placed in the saxlet apparatus. About 300 ml of HPLC-grade n-heptane is poured into a round bottom flask with stir bar and the flask is fixed on a heating mantle. Connect round bottom flasks, sacks and condensers in series. More n-heptane was poured through the center of the condenser into the soxlet main chamber until the amount of solvent was just below the top of the overflow tube. The cooling water was turned to the condenser. The heating mantle was turned on and settings were adjusted to produce rolling heating and maintain good reflux in the round bottom flask. Reflux for 16 hours. Turn off the heat and leave the cooling system on. Allow the system to cool to room temperature. Dismantle the device. Remove the dumble and rinse with a small amount of fresh n-heptane. Air dry in a laboratory hood and oven dry at 95 ° C. for 90 minutes. The tumble containing the polymer is weighed immediately after being taken out of the oven and recorded as C: Later Polymer / Dimble Weight (g).

The amount of extract is determined by calculating the weight loss from the sample. W = (A + B-C) (g). The extractable amount (E, weight%) is calculated by the formula E = 100 (W / B). The plasticizer content (P, wt%) in the mixture is calculated by P = E (mixture) -E (base polymer).

Method 2: Crystallization Analysis Fractionation (CRYSTAF)

Another method to determine the amount of NFP in the mixture is to fractionate using Crystallization Assay Fractionation (CRYSTAF) technique. This technique involves dissolving the sample at high temperature in a solvent and slowly cooling the solution to induce fractionation of the sample based on solubility. For semicrystalline samples, including mixtures, the solubility depends primarily on the crystallization capacity. That is, the more crystalline sample portion will precipitate out of solution at a higher temperature than the less crystalline sample portion. The relative amount of sample in solution as a function of temperature is measured using an infrared (IR) detector to obtain a cumulative solubility distribution. Soluble fraction (SF) is defined as the IR signal at the lowest temperature divided by the IR signal when all samples are dissolved at high temperatures, which corresponds to the weight fraction of the sample that is not crystallized.

For plasticized polyolefins, plasticizers are mostly amorphous and contribute to SF. Thus, SF will be larger for mixtures with higher plasticizer content. This relationship is used to determine the plasticizer content of a mixture of known (polymer and plasticizer type) compositions except for unknown concentrations. The calibration curve, which describes SF as a function of plasticizer content, is used to prepare a series of physical mixtures of known concentrations using the same polymer and plasticizer material, and to analyze these mixtures under the same performance conditions as used for mixtures of unknown concentrations. Is created. This series of calibrants must have a plasticizer concentration of only 50% by weight or less above and below the concentration of the unknown sample in order to reliably apply the assay curve to the unknown sample. In general, it was found that SF was well described as a function of plasticizer content (R ² > 0.9) by taking the calibration points linearly. Other functional forms with two or fewer creation factors can be used if they improve the goodness of fit (increasing R ² ).

This test was performed using a commercial CRYSTAF 200 instrument (Polymer Char S. A., Valencia, Spain) with 60 ml of five stirred stainless steel vessels. About 30 mg of the sample was dissolved for 60 minutes at 160 ° C. in 30 ml of 1,2-dichlorobenzene stabilized with 2 g / 4 L of butylated hydroxytoluene. This solution was stabilized at 100 ° C. for 45 minutes. Crystallization was performed at 100 to 30 ° C. at a crystallization rate of 0.2 ° C./min. Polymer concentrations in solution were measured at regular intervals during the crystallization cycle using a dual wavelength infrared detector with heated flow through the cell maintained at 150 ° C. The measured wavelength was 3.5 탆 and the reference wavelength was 3.6 탆.

The invention may be better understood with reference to the following examples and tables, which are not intended to limit the invention.

Examples prepared using the extruder method

Samples 1-9 were mixed using the extruder method. The additive package contained 600 ppm Irganox 1076 and 260 ppm calcium stearate and a 57 mm twin screw extruder was used at an extrusion temperature of 230 ° C. Samples 10-14 were mixed using an extruder method. The additive package contained 825 ppm calcium stearate, 800 ppm Ultranox 626, 500 ppm Tinuvin 622, and 2500 ppm Millad 3940. A 30 mm twin screw extruder was used at an extrusion temperature of 216 ° C. Samples 15-19 were mixed using the extruder method. The additive package contained 800 ppm calcium stearate, 1500 ppm Irganox 1010, 500 ppm Ultranox 626, and 675 ppm sodium benzoate. A 30 mm twin screw extruder was used at an extrusion temperature of 205 ° C. Samples 21-24 were prepared by anhydrous mixing of premixed pellets of high plasticizer concentration (Samples 6-9) and pure polymer pellets to achieve the desired plasticizer concentration.

The resin properties of these samples are listed in Tables 6-8. The addition of NFP in the propylene polymer improves melt flowability, as indicated by the significant increase in melt flow rate. The improvement in melt flowability is characterized by a decrease in shear viscosity as a function of the shear rate range as shown in FIGS. 11-13. In contrast to the peroxide decomposition (or "bisbreaking") process, the increase in melt flowability of the present invention is mainly due to the plasticizing effect of NFP and the polymer molecular weight does not change. This is evidenced by comparison of the molecular weight distribution as shown in FIG. 14. Improved melt flow typically results in better draw-down, lower extruder torque, thinner wall injection, and faster cycles in the fabrication process (eg fiber spinning, film casting, extrusion and injection molding). It is advantageous in terms of.

In the present invention, NFP significantly reduces the storage modulus of propylene polymers. As explained in FIG. 1, the storage modulus of the plasticized propylene polymer is drastically reduced as a function of temperature compared to the unplasticized polyolefin. Propylene polymers having a lower storage modulus (or “elastic modulus”) at any particular temperature show better flexibility for end use at certain temperatures.

NFP in the present invention illustrates the ability to drop Tg without changing the melting and crystallization temperatures of the propylene polymer, as shown in FIGS. Traditional methods of lowering Tg include the introduction of comonomers as in the case of propylene copolymers, which also lower the melting point and crystallization temperature of the polymer. Polymers having lower Tg without degrading the melting properties are highly desirable and provide better impact resistance, in particular impact resistance below freezing point, while maintaining the ability for high temperature applications. The plasticized polyolefins of the present invention provide this advantage.

In the present invention, the NFP is miscible with the propylene polymer, for example as determined by the single Tg profile of the plasticized propylene homopolymer and the propylene copolymer. This is shown graphically in FIGS. 2 and 3. In the present invention, NFP is determined by two Tg profiles of the plasticized propylene impact copolymer (ie one is the lower Tg profile on the ethylene propylene rubber and the other is the higher Tg profile on the propylene polymer). As can be mixed with the propylene impact copolymer. This is shown graphically in FIG. 4.

The injection molded properties of these samples are summarized in Tables 9-11. Parts molded from the plasticized polypropylene homopolymers of the present invention, while maintaining their tensile strength, room temperature izod impact resistance and heat deflection temperature, have a significant reduction in flexural and tensile modulus at a loading of 4% by weight PAO or isoparaffin. Indicates. For comparison, molded samples were prepared using erucamide (cis-13-dococenoamide from chrometon), a conventional lubricant designed to reduce molded part surface friction at a concentration of 4% by weight. The effect of erucamide on flexural modulus is not large as shown in Table 11.

The addition of NFP substantially improves the impact resistance of the molded part without a significant reduction in heat distortion temperature. For example, at room temperature and freezing point Gardner impact strength is 350-400% for propylene homopolymer, 140-165% for propylene copolymer, for propylene impact copolymer due to the addition of 4-5% by weight of NFP 20 to 40% improvement. It is expected that a further increase in impact resistance can be achieved by increasing the NFP concentration in the propylene polymer. Other measurements of impact resistance, including Izod impact at room temperature and freezing point, have also been significantly improved.

Another advantage of the present invention is that the heat deflection temperature of the plasticized polyolefin, which is important for applications where maintenance of molded article dimensions at high temperatures is required (or is maintained or only slightly reduced). Toughness improvement is further indicated by a significant increase in elongation at yield and breakdown. Many applications require good conformance during end use. Higher elongation allows the molded article to easily adapt to deformation during the conversion process or end use.

NFP also exhibits the ability to provide substantial softening improvements in spunbonded nonwoven fabrics, as given by the lower "total hand" in Table 12. In many applications, especially in the field of personal hygiene and health care, soft nonwovens are highly desirable for comfortable skin contact. The present invention not only provides an improvement in ductility but also maintains the required tensile strength, crack resistance and fabric uniformity.

A comparison of the film properties is shown in Table 13. NFP, in particular Isopar-V plasticized propylene homopolymer (Sample 2), is relatively high (relative to unplasticized polyolefin) in Emendorf crack, room temperature and freezing point both in the machine direction (MD) and in the transverse direction (TD). As indicated by the dart impact, it provides an improvement in crack and impact resistance. In addition, optical properties, ie haze and glossiness, are improved. These improvements provide advantages for many film applications, such as food packaging, stationery covers, tapes, medical and electronic packaging.

The data in Tables 25 and 26 show similar advantages. The fluidity is improved by the additive of NFP, as shown by the increase of MFR. Toughness increases as evidenced by the increase in impact properties. Ductility increases, as can be seen by the decrease in flexural modulus, but HDT is not significantly affected. While the Tg drop is significant, the melting point and crystallization point remain substantially unchanged (up to 1-2 ° C.).

Plasticizer permanence

Loss of plasticizer as a function of time at elevated temperature provides a method for evaluating the plasticizer's permanence. The results in Table 27 for plasticized propylene random copolymers demonstrate the importance of the molecular weight of the plasticizer. Plasticizers were PAO liquids and white inorganic oils that increased the molecular weight. Each plasticized sample was prepared by anhydrous mixing granules of propylene polymer with 10% by weight plasticizer and pellets were melt mixed using a single screw extruder. Some were compression molded into 0.25 mm thick sheets for release tests performed according to ASTM D1203. The test piece was 50 mm in diameter. The test temperature was 70 ° C. Test pieces were weighed at 0, 24, 48. 139, 167, and 311 hours and the percent weight loss was calculated. As a result of the observation over a long time, only the highest molecular weight PAO showed no additional weight loss than that observed for the pure polymer. Notably, inorganic oils exhibit significantly lower permanence than comparable KV PAO liquids at 100 ° C. (> 5 wt% loss vs. 1-2 wt% loss for PAO at 311 hours).

Examples Prepared Using the Brabender Method

The samples shown in Tables 15-24 were mixed using the Brabender method. The data in these tables show similar advantages as those in Tables 6-13. Fluidity is enhanced by the addition of NFP, as evidenced by the increase in MFR. Low temperature toughness increases as evidenced by the rise in notched izod at 18 ° C. Ductility is improved, as can be seen from the drop in flexural modulus. While the Tg drop is significant, the melting point and crystallization point do not substantially change (to within 1-2 degrees C.).

While the invention has been described and described with reference to specific embodiments, those skilled in the art will understand that the invention can be applied to many different variations that are not described herein. For this reason, reference should only be made to the scope of the appended claims in order to determine the scope of the invention. Certain features of the invention are also described by a series of numerical upper limits and a series of numerical lower limits. It is to be understood that the range formed by any combination of these limits is within the scope of the present invention unless otherwise indicated.

All preceding documents are hereby incorporated by reference in their entirety under the authority to allow introduction of such documents. In addition, all documents, including the test procedures cited herein, are incorporated by reference in their entirety under the authority to permit the introduction of such documents.

Claims (78)

A plasticized polyolefin composition comprising at least one polyolefin and at least one non-functionalized plasticizer (NFP) having a kinematic viscosity (“KV”) at 100 ° C. of 2 cSt or less. The method of claim 1, The composition wherein the non-functionalized plasticizer comprises at least 50% by weight of C ₆ to C ₁₀₀ isoparaffin. The method of claim 1, Wherein the non-functionalized plasticizer comprises at least 50% by weight of C ₅ to C ₂₅ n-paraffins having less than 0.1% aromatics. The method of claim 1, And wherein the non-functionalized plasticizer comprises at least 50% by weight of dearomatized aliphatic hydrocarbon comprising a mixture of normal paraffins, isoparaffins and cycloparaffins. The method of claim 1, And wherein the non-functionalized plasticizer comprises at least 50% by weight of dearomatized aliphatic hydrocarbons comprising a mixture of C ₄ to C ₂₅ normal paraffins, C ₄ to C ₂₅ isoparaffins and C ₄ to C ₂₅ cycloparaffins. A plasticized polyolefin composition comprising at least one polyolefin and at least one non-functionalized plasticizer comprising C ₂₀ to C ₁₅₀₀ paraffins having a kinematic viscosity of at least 10 cSt and a viscosity index of at least 120 at 100 ° C. A plasticized polyolefin composition comprising at least one polyolefin and at least one non-functionalized plasticizer comprising oligomers of C ₅ to C ₁₄ olefins having a kinematic viscosity of at least 10 cSt and a viscosity index of at least 120 at 100 ° C. A plasticized polypropylene composition comprising polypropylene and at least one non-functionalized plasticizer comprising an oligomer of C ₆ to C ₁₄ olefins having a viscosity index of at least 120, wherein the plasticized composition has from 8 to 12 carbon atoms Plasticizing, which comprises 4 to 10% by weight of a hydrogenated, highly branched dimer of alpha alpha olefin, polyalphaolefin, wherein the composition does not comprise 18 to 25% by weight of linear low density polyethylene having a density of 0.912 to 0.935 g / cc. Polypropylene composition. A plasticized polypropylene composition comprising polypropylene and at least one non-functionalized plasticizer comprising an oligomer of C ₆ to C ₁₄ olefins having a viscosity index of at least 120, wherein the composition is 40 to 50 weight percent polypropylene. A plasticized polypropylene composition comprising no impact copolymer of% ethylene propylene rubber, or wherein the composition does not comprise a random copolymer of propylene and ethylene. The method according to any one of claims 6 to 9, Wherein said non-functionalized plasticizer comprises an oligomer of decene having from 40 to 200 carbon atoms. The method according to any one of claims 6 to 10, Wherein said non-functionalized plasticizer comprises an oligomer of 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undodecene and / or 1-dodecene. The method according to any one of claims 6 to 11, Wherein said non-functionalized plasticizer comprises an oligomer of decene having a carbon number of from 200 to 1500. The method according to any one of claims 6 to 12, Wherein said non-functionalized plasticizer has a kinematic viscosity of 10 cSt at 100 ° C. The method according to any one of claims 6 to 13, Wherein said non-functionalized plasticizer has a viscosity index (VI) of at least 130. A plasticized polyolefin composition comprising a polyolefin and a non-functionalized plasticizer comprising an inorganic oil having a saturate level of at least 90%, a sulfur content of 0.03% or less and a VI of at least 120. Plasticized polyolefin composition comprising a polyolefin and a non-functionalized plasticizer comprising a mixture of branched and normal paraffins having a branched paraffin to n-paraffin ratio of from 6 to 50 carbon atoms and from 0.5: 1 to 9: 1 . The method of claim 16, Wherein said mixture comprises more than 50% by weight mono-methyl species. The method according to claim 16 or 17, Wherein said plasticizer comprises a mixture of branched and normal paraffins having a branched paraffin to n-paraffin ratio of from 10 to 16 carbon atoms and from 1: 1 to 4: 1. At least one polyolefin and a linear or branched paraffinic hydrocarbon composition having a number average molecular weight of 500 to 20,000, less than 10% of side chains having at least 4 carbons and at least 1 or 2 carbon branches present at least 15% by weight. A plasticized polyolefin composition comprising at least one non-functionalized plasticizer (NFP), wherein the NFP comprises less than 2% by weight of cyclic paraffins. At least one polyolefin, and having a number average molecular weight (Mn) of 15,000 and a weight average molecular weight (Mw) of 60,000 or less, 1) a copolymer of C ₄ raffinate, 2) poly (n-butene), or 3) at least isobutyl A plasticized polyolefin composition comprising at least one non-functionalized plasticizer comprising a copolymer of lene derived units, 1-butene derived units, and 2-butene derived units. The method according to any one of claims 1 to 20, The composition being less than 1% by weight when the plasticized composition is stored at 70 ° C. for 312 hours in a drying oven. The method according to any one of claims 1 to 21, The non-functionalized plasticizer is a functional group selected from the group consisting of hydroxide, aryl and substituted aryl, halogen, alkoxy, carboxylate, ester, carbon unsaturated, acrylate, oxygen, nitrogen and carboxyl based on the weight of NFP To 0.1% by weight or less. The method according to any one of claims 1 to 22, A composition having a glass transition temperature (Tg) of less than 30 ° C. even if the non-functionalized plasticizer cannot or cannot be measured. The method according to any one of claims 1 to 23, Wherein said non-functionalized plasticizer has a distillation range having a difference between an upper temperature and a lower temperature of 20 ° C. or less. The method according to any one of claims 1 to 24, Wherein said non-functionalized plasticizer has an initial boiling point greater than 110 ° C. The method according to any one of claims 1 to 25, Wherein said non-functionalized plasticizer has a pour point of -15 ° C. or less. The method according to any one of claims 1 to 26, Wherein said non-functionalized plasticizer has a specific gravity of less than 0.86. The method according to any one of claims 1 to 27, Wherein said non-functionalized plasticizer has a specific gravity of 0.70 to 0.86. The method according to any one of claims 1 to 28, Said non-functionalized plasticizer having a final boiling point of from 115 to 500 ° C. The method according to any one of claims 1 to 29, Wherein said non-functionalized plasticizer has a weight average molecular weight of 2,000 to 100 g / mol. The method according to any one of claims 1 to 30, Wherein said non-functionalized plasticizer has a flash point between -30 and 350 ° C. The method of any one of claims 1 to 31, The non-functionalized plasticizer has a dielectric constant of less than 3.0 at 20 ° C. The method according to any one of claims 1 to 32, Wherein said non-functionalized plasticizer has a density of 0.70 to 0.83 g / cm 3. The method according to any one of claims 1 to 33, Said non-functionalized plasticizer having a viscosity of 0.5 to 20 cSt at 25 ° C. The method according to any one of claims 1 to 34, Wherein said non-functionalized plasticizer has 6 to 150 carbon atoms. The method according to any one of claims 1 to 35, Wherein said non-functionalized plasticizer has 7 to 100 carbon atoms. The method according to any one of claims 1 to 36, Wherein said non-functionalized plasticizer has 10 to 30 carbon atoms. The method according to any one of claims 1 to 37, Said non-functionalized plasticizer having 12 to 25 carbon atoms. The method according to any one of claims 1 to 38, A composition having a single glass transition temperature lower than the polyolefin itself. 40. A compound according to any one of the preceding claims, And T _g is at least 4 ° C. lower than the pure polyolefin. The method according to any one of claims 1 to 40, T _g is at least 10 ° C. lower than pure polyolefin. The method according to any one of claims 1 to 41, T _g is at least 15 ° C. lower than pure polyolefin. 33. The method according to any one of claims 30 to 32, The peak melting point of the pure polyolefin is within 1 to 4 ℃ of the plasticized polyolefin composition. The method according to any one of claims 30 to 33, wherein Wherein the crystallization temperature of the pure polyolefin is within 1 to 4 ° C. of the plasticized polyolefin. The method according to any one of claims 1 to 44, Wherein the polyolefin comprises polypropylene. The method according to any one of claims 1 to 45, Wherein the polyolefin comprises isotactic polypropylene. The method according to any one of claims 1 to 46, Wherein the polyolefin comprises syndiotactic polypropylene. 48. The compound of any of claims 1 to 47, wherein Wherein the polyolefin comprises a high isotactic polypropylene. 49. The compound of any one of the preceding claims, Wherein the polyolefin comprises isotactic polypropylene. The method according to any one of claims 1 to 49, Wherein the polyolefin comprises an impact copolymer. The method according to any one of claims 1 to 50, The polyolefin further comprises an elastomer. The method according to any one of claims 1 to 51, The polyolefin further comprises a plastomer. The method of any one of claims 1-52, The polyolefin has a Mw of 30,000 to 1,000,000 g / mol. The method of any one of claims 1-53, The polyolefin has a Mw / Mn of 1.6 to 10. The method of any one of claims 1-54, The polyolefin has a melting point (second melt) of 30 to 185 ° C. The method according to any one of claims 1 to 55, The polyolefin has a crystallinity of 5 to 80%. The method according to any one of claims 1 to 56, The polyolefin has a heat of fusion of 20 to 150 J / g. The method according to any one of claims 1 to 57, Wherein the polyolefin has a Gardner impact strength of 20 in-lb to 1000 in-lb when measured on a 0.125 inch disk at 23 ° C. The method according to any one of claims 1 to 58, Wherein the polyolefin has a 1% secant flexural modulus of between 100 and 2300 MPa. The method according to any one of claims 1 to 59, Wherein the polyolefin has a melt flow rate of 0.3 to 500 dg / min. 61. The method of any of claims 1 to 60, Polyolefins are ethylene, butene, pentene, hexene, heptene, octene, nonene, decene, dodecene, 4-methylpentene-1, 3-methylpentene-1, 5-ethyl-1-nonene and 3,5,5- A composition comprising a copolymer of propylene with 0.5-30% by weight of one or more comonomers selected from the group consisting of trimethyl-hexene-1. The method of any one of claims 1 to 61, Polyolefin comprises propylene, 0 to 5% by weight diene and 2 to 25% by weight ethylene based on the total weight of the polymer, narrow composition distribution, melting point (Tm) of 25 to 120 ℃, 50 to 3 J / g Heat of fusion, Mw / Mn of 1.5 to 5 and a melt index (MI) of less than 20 dg / min. 651. The method of claim 642 The polyolefin has a stereoregularity index of 4 to 12. The method of any one of claims 1 to 63, wherein Wherein the polyolefin is present at 50 to 99.99% by weight, based on the weight of the polyolefin and the non-functionalized plasticizer. 65. The method of any of claims 1-64, Wherein said non-functionalized plasticizer is present at 0.5 to 35 weight percent, based on the weight of the polyolefin and non-functionalized plasticizer. The method of any one of claims 1 to 65, Wherein said non-functionalized plasticizer is present at 1 to 15 weight percent, based on the weight of the polyolefin and the non-functionalized plasticizer. 67. The method of any of claims 1-66, A propylene impact copolymer or blend wherein the polyolefin comprises from 40 to 95 weight percent of component A and from 5 to 60 weight percent of component B, based on the total weight of the copolymer, wherein component A comprises 10 ethylene, butene, hexene or octene comonomers. A propylene copolymer or homopolymer comprising up to weight percent, component B comprising a propylene copolymer comprising 5 to 70 weight percent ethylene, butene, hexene and / or octene comonomer and 95 to 30 weight percent propylene Composition. The method of claim 67 wherein And wherein the refractive index of component A and component B are within 10% of each other, and optionally the refractive index of the non-functionalized plasticizer is within 20% of component A, component B, or both. The method of any one of claims 1 to 68, A composition substantially free of polyethylene having a weight average molecular weight of 500 to 10,000 and / or substantially free of phthalates, adipates, trimellitate esters and polyesters. 70. The method of any of claims 1-69, A composition comprising a segment wherein the polyolefin is isotactic. 70. An article comprising the composition of any of claims 1-70. The method of claim 71 wherein Cookware, Storage Appliances, Furniture, Automotive Components, Boat Components, Toys, Sportswear, Medical Devices, Sterilization Containers, Nonwoven Textiles, Nonwoven Fabrics, Drapes, Gowns, Filters, Hygiene Products, Diapers, Films, Orientation Films, Sheets , Tubes, pipes, fibers, woven fabrics, sports equipment, plumbing, wire jackets, cable jackets, agricultural films, geomembrane, bumpers, grills, trim parts, instrument panels, instrument panels, exterior door components, hood components Spoilers, wind screens, wheel caps, mirror housings, body panels, protective side moldings, boxes, containers, packaging, laboratory equipment, office floor mats, metrology sample holders, sample windows; Liquid storage containers, bags, pouches, bottles for storage and IV infusion of blood or solutions; A product selected from the group consisting of packaging materials for any medical device or drug, including unit-dose, blister packs, bubble packs, adhesives, soles, gaskets, corrugations, elastic fibers and sealants. The composition according to any one of claims 1 to 70, which is injection molding, compression molding, transfer molding, casting, extrusion, thermoforming, blow molding, spunbonding, melt blowing, lamination, drawing, fiber spinning, draw reduction reduction, rotational molding, spin bonding, melt spinning, or a combination thereof. 70. A nonwoven product comprising the composition of any of claims 1-70. 71. A method of making a nonwoven article comprising meltblown, spunbonding, film perforating and / or staple fiber carding the composition of any of claims 1-70. 70. A fiber comprising a composition according to any one of claims 1 to 70 is extruded through a spinneret, the fiber is drawn using high velocity air, and the drawn fiber is placed on an endless belt to form a web. And bonding the fibers together. And polymerizing the polyolefin in a solution method and introducing a non-functionalized plasticizer soluble in the solvent medium into the polymer solution prior to removing the solvent. 16. A process for preparing plasticized polyolefins comprising polymerizing polyolefins in bulk and introducing a soluble non-functionalized plasticizer in bulk medium into the polymer solution prior to removing the solvent.