JP2006193719A - Syndiotactic rich polyolefins - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a good adhesive polyolefin and good adhesive resin compositions containing the polymer. <P>SOLUTION: A polymer comprising an amorphous syndiotactic rich polyolefin which comprises not less than about 50 percent by weight of a 3-40C alpha olefin, has about 50% to about 80% r dyads, based on the total number of r and m dyads present in the polymer and exhibits a heat of fusion of 10 J/g or less according to the procedure described in ASTM E794-85 and an ash content of 1 percent by weight or less is provided. A functionalized amorphous syndiotactic rich polyolefin is also preferred. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

Detailed Description of the Invention

Related Application This application claims the benefit of provisional application No. 60 / 622,964, filed Oct. 28, 2004. This application is a continuation-in-part of US Patent Application No. 10/825348, filed on April 15, 2004.

FIELD OF THE INVENTION The present invention relates to polymers, polymer compositions, adhesive compositions, and / or adhesive additives, and amorphous syndiotactic rich polyolefin olefins and / or functional amorphous syndiotactic rich polyolefins. Including these manufacturing methods. In particular, the polymer may include a polypropylene rich in amorphous syndiotactic and / or a polypropylene rich in amorphous syndiotactic maleate and may be in combination with one or more additives.

BACKGROUND OF THE INVENTION Olefin-based polymers (polyolefins) are widely used in a variety of applications due to their chemical inertness, low density and low price. Typical applications include applications relating to adhesives, tie layers, films, fibers, materials, laminates and combinations thereof.

  Polyolefins can be formed into various films, can be laminated to various substrates, coated, or coextruded. Films and substrates can be mixed with other materials to form a structure having multiple layers, each layer having a specific purpose. The packaging laminate can include, for example, multiple layers, eg, a structurally rigid core layer made of paper or paperboard, an outer liquid tight layer, an oxygen gas barrier such as an aluminum foil intermediate layer, and / or application needs. It is other layer according to.

  To obtain effective adhesion, it is preferable to achieve excellent bond strength or tight bonding between layers in most applications. However, relatively non-polar olefin-based polymers do not usually adhere well to more polar substrates.

  Accordingly, there is a need for adhesives that tightly bond both polar and non-polar substrates, preferably those exhibiting excellent bond strength durability under various temperature conditions and in the presence of active substances.

  Further, to function as a tie layer or other adhesive, the adhesive composition is adhesive between various polar and non-polar substrates within a “relatively” temperature range of about −20 ° C. to about 10 ° C. There is a need to show. However, polyolefins usually lack adhesive properties at this relatively low temperature range. Also, the adhesive composition should be soluble in various solvents to facilitate the use of the adhesive on the substrate. However, most polyolefins that exhibit adhesive properties have crystallization levels that hinder dissolution in common hydrocarbon solvents. Accordingly, adhesive promoters can be utilized with various adhesive compositions to improve the bonding, adhesion and other properties aspects of the adhesive.

  For example, US Pat. No. 6,656,385, Wang, et al. (Wang) added tackifiers, optionally plasticizers and / or stabilizers with about 70% syndiotactic polypropylene and amorphous poly (α-olefin). Containing hot melt adhesive. Wang defines syndiotactic polypropylene as having over 70% r dyads. As such, Wang does not disclose syndiotactic polypropylene that is essentially soluble in hydrocarbon solvents.

  U.S. Pat. No. 4,822,688, Nogues is an adhesive composition comprising polypropylene modified by grafting with an acid anhydride, further reacting with a compound carrying at least two groups such as polyols or polyamines It is related with the made adhesive composition. Nogues discloses functional polyolefins, but the document does not disclose polyolefin adhesion promoters rich in functional amorphous syndiotactic that improve adhesion, solubility and processability.

  Numerous references are aimed at compositions containing syndiotactic polypropylene as an adhesive promoter. Examples include Japanese Patent Application Publication No. 01-152448, Japanese Patent No. 2824082, U.S. Pat. Nos. 5,476,914, 6,184,326 and 6,245,870. And a vanadium catalyst capable of producing a composition comprising syndiotactic polypropylene having an r dyad greater than or equal to 80%. However, the crystallinity of the syndiotactic rich polypropylene according to the document prevents the substance from dissolving in the hydrocarbon solvent, thus limiting the use of the substance. In addition, these references are aimed at the specific growth of syndiotactic under "catalytic site control", resulting in "rmmr" fragments in the polymer produced. This is in contrast to the “chain end control” of the present invention, which produces an “rrmr” fragment and essentially no “rmmr” fragment.

  U.S. Pat. Nos. 5,326,824, 5,373,059, 5,374,685 and Japanese Patent No. 3025553 relate to compositions comprising functional syndiotactic polypropylene. However, the functional syndiotactic polypropylene disclosed in these references has a crystallinity higher than about 50% (eg, [rrrr]> 50%, more preferably [rrrr]> 70%) and therefore The polymer thus produced is insoluble in organic solvents.

  Japanese Patent No. 2837246 has [rrrr]> 80%, intrinsic viscosity of about 0.01 to 10 dl / g, Mw / Mn of 1.5 to about 20, melting temperature Tm of about 130 to 170 ° C. And syndiotactic polypropylene with t1 / 2 = 2 minutes. The polymer produced according to patent 2837246 is therefore crystalline, has a melting temperature and is not soluble in organic solvents.

  In addition, syndiotactic polypropylene produced using a vanadium-based catalyst yields a material having an ash content of about 1% by weight or more due to residual material from the catalyst present, as measured herein.

  Accordingly, polymers and polymer compositions comprising polyolefins rich in syndiotactic and / or polyolefins rich in functional syndiotactic, which are essentially soluble in various protein solvents at room temperature, preferably There remains a need for polymers and polymer compositions that have an ash content of less than 1% by weight. As such, with low crystallinity, eg, syndiotactic rich polyolefins with [rrrr] <50%, there is no clear melting temperature and / or a heat of fusion of less than about 10 J / g There remains a need for polyolefins rich in functional syndiotactic.

SUMMARY OF THE INVENTION In one aspect of the invention, the polymer comprises about 50% by weight or more of C3-C40α olefin, and about 50% to about 80% r based on the total number of r and m dyads present in the polymer. Amorphous syndiotactic rich polyolefins having a dyad, a heat of fusion of 10 J / g or less, and an ash content of 1 wt% or less according to the procedure described in ASTM E 794-85.

  In another aspect of the invention, the polymer blend is about 50% or more C3-C40α olefin, about 50% to about 80% r dyad based on the total number of r and m dyads present in the polymer, heat of fusion. Comprising an amorphous syndiotactic rich polyolefin having a ash content of not more than 10 J / g and an ash content of not more than 1% by weight according to the procedure described in ASTM E 794-85, and C2-C40 polymers, C2-C40 copolymers, Elastomer, random copolymer, impact copolymer, functional polymer, tackifier, crosslinking agent, antioxidant, neutralizer, nucleating agent, filler, adhesion promoter, oil component, plasticizer, wax, ester polymer, rubber reinforcement Composition, recycled polymer, blocking agent, antiblocking agent, pigment, dye, processing aid, UV stabilizer, moisture Including, adjuvants, surfactants, color masterbatches, flow improvers, crystallization aids, or at least one additive comprising a combination of these.

  In yet another aspect of the invention, the polymer comprises a polyolefin rich in amorphous syndiotactic functionalized with functional groups, wherein the polyolefin rich in amorphous syndiotactic before functionalization is From about 50% to about 80% by weight C3-C40α olefin, from about 50% to about 80% r dyad, based on the total number of r and m dyads present in the polymer, the heat of fusion described in ASTM E 794-85 According to the procedure, 10 J / g or less and the ash content is 1% by weight or less.

  In yet another aspect of the invention, the polymer blend includes a polyolefin rich in amorphous syndiotactic functionalized with a functional group, wherein the polyolefin rich in morphological syndiotactic before functionalization. Contains about 50% by weight or more C3-C40α olefin, contains about 50% to about 80% r dyads based on the total number of r and m dyads present in the polymer, and the heat of fusion is ASTM E 794-85. 10 J / g or less, an ash content of 1% by weight or less, and a C2-C40 polymer, a C2-C40 copolymer, an elastomer, a random copolymer, an impact copolymer, a functional polymer, a tackifier, a crosslinking agent, Antioxidants, neutralizers, nucleating agents, fillers, adhesion promoters, oils, plasticizers, waxes Ester polymer, rubber reinforcing composition, recycled polymer, blocking agent, antiblocking agent, pigment, dye, processing aid, UV stabilizer, lubricant, auxiliary agent, surfactant, color masterbatch, fluidity improver, At least one additive comprising a crystallization aid, or a combination thereof.

  In another aspect of the invention, the invention is a contact product of an amorphous syndiotactic rich polyolefin, a functional group, and a functionalized catalyst, wherein the amorphous syndiotactic rich polyolefin is about Contains 50 wt% or more of C3-C40α olefin, contains from about 50% to about 80% r dyad based on the total number of r and m dyads present in the polymer, and the heat of fusion is described in ASTM E 794-85 And 10 J / g or less, and the ash content is 1 wt% or less.

  In another aspect of the invention, the polymer comprises a polypropylene rich in amorphous syndiotactic functionalized with maleic anhydride, wherein the functionalized polypropylene accounts for the total number of r and m dyads present in the polymer. Based on about 50% to about 80% r dyad, with a heat of fusion of 10 J / g or less according to the procedure described in ASTM E 794-85, and an ash content of 1% by weight or less.

  In yet another aspect of the invention, the polymer blend includes a polypropylene rich in amorphous syndiotactic functionalized with maleic anhydride and at least one additive, wherein the functionalized polypropylene is present in the polymer. About 50% to about 80% of the r dyad based on the total number of r and m dyads to be performed, the heat of fusion is 10 J / g or less according to the procedure described in ASTM E 794-85, and the ash content is 1 weight %, And where additives are C2-C40 polymer, elastomer, random copolymer, impact copolymer, functional polymer, tackifier, crosslinker, antioxidant, neutralizer, nucleating agent, filler Agent, adhesion promoter, oil, plasticizer, wax, ester polymer, blocking agent, antiblocking agent, pigment, dye, processing It is selected from the group consisting of auxiliaries, UV stabilizers, lubricants, auxiliaries, surfactants, color masterbatches, flow improvers, crystallization aids, and combinations thereof.

  In another aspect of the invention, the adhesive composition comprises an amorphous syndiotactic rich polyolefin, an amorphous syndiotactic rich polyolefin functionalized with functional groups, or a combination thereof, wherein the amorphous composition is amorphous. The syndiotactic rich polyolefin contains about 50% by weight or more of C3-C40α olefin, and contains about 50% to about 80% r dyad based on the total number of r and m dyads present in the polymer. The heat of fusion is not more than 10 J / g according to the procedure described in ASTM E 794-85 and the ash content is not more than 1% by weight, where the functional group, if present, has a weight average molecular weight of not more than 1000. Containing compounds, and carbon-carbon double bonds, carbon-carbon triple bonds, and / or heteroatoms An adhesive composition having a peel strength of about 3.5 lb / inch or more for isotactic polypropylene and a peel strength of about 0.5 lb / inch for a polyester film, wherein a 0.5 inch wide sample and 2 ″ / Measured according to ASTM D-1876, modified to use a minute separation rate.

  In yet another aspect of the invention, the polymer comprises a polyolefin rich in amorphous syndiotactic functionalized with a functional group, wherein the polyolefin rich in functionalized amorphous syndiotactic is about 50 wt. The procedure according to ASTM E 794-85, comprising about 50% to about 80% r dyad, based on the total number of r and m dyads present in the polymer According to the above, 10 J / g or less.

  In another aspect of the invention, a method of making a polymeric material includes 10-90 wt% polyolefin by melt blending an amorphous syndiotactic rich polyolefin and at least one additive under high shear conditions. Producing a concentrate and subsequently blending the concentrate with at least one additional material to produce a final product, wherein the amorphous syndiotactic rich polyolefin is about Contains 50 wt% or more of C3-C40α olefins, contains from about 50% to about 80% r dyads based on the total number of r and m dyads present in the polyolefin, the heat of fusion described in ASTM E 794-85 And 10 J / g or less, and the ash content is 1 wt% or less.

In another aspect of the invention, a method of producing a polyolefin rich in functional amorphous syndiotactic comprising the following steps:
A. Adding an olefin monomer, a metallocene catalyst and an activator into the aliphatic solvent of the reactor;
B. Performing a catalyst solution polymerization of the olefin monomer in the reactor to produce a polyolefin rich in amorphous syndiotactic;
C. Removing the monomer to remove unreacted olefin monomer;
D. The amorphous syndiotactic rich polyolefin, functional group and free radical initiator in the aliphatic compound solvent at a temperature and for a time sufficient to produce the functional amorphous syndiotactic rich polyolefin. Performing solvent-based functionalization, including mixing; Removing the aliphatic compound solvent;
Here, rich polyolefin amorphous syndiotactic, C ₃ -C ₄₀ alpha-olefin of at least about 50 wt%; about, based on the total number of r and m dyads present in the polyolefin 50% to about 80% An r dyad of 10 J / g or less according to the procedure described in ASTM E 794-85; and an ash content of 1% by weight or less.

In another aspect of the invention, a method of producing a polyolefin rich in functional amorphous syndiotactic comprising the following steps:
A. Adding a melt containing a polyolefin rich in amorphous syndiotactic, functional groups, and a free radical initiator to a mixing device;
B. Contacting the lysate in the mixing apparatus at a temperature and for a time sufficient to produce a polyolefin rich in the functional amorphous syndiotactic, wherein the amorphous syndiotactic rich polyolefins is greater than about 50% by weight of _C 3 _{-C 40} alpha-olefin; based on the total number of r and m dyads present in the polyolefin of from about 50% to about 80% r dyads, heat of fusion ASTM E 794- 85 or less according to the procedure described in 85; and an ash content of 1% by weight or less.

  Various products containing the polymer with the blend of polymers are also disclosed.

Definitions For purposes of the present invention and claims, and for ease of reference, olefins present in a polymer and / or oligomer are referred to as included, contained, etc. It is a polymerization form of olefin. For simplicity of reference, the amorphous polyolefin polymer is aPP, the isotactic rich polyolefin polymer is irPP, the syndiotactic rich polyolefin polymer is srPP, and the amorphous syndiotactic rich polyolefin polymer is a- srPP, semicrystalline polyolefin polymer is abbreviated to scPP, and "Xg-FG" indicates that component X is grafted (-g-) with functional group "FG".

  For purposes of this disclosure, the term oligomer refers to a composition having 2 to 40 mer units and the term polymer refers to a composition having 41 or more mer units. A mer is defined as an oligomer or polymer unit that naturally corresponds to the monomer used in the oligomerization or polymerization reaction. For example, the polyethylene mer is ethylene. For simplicity, unless otherwise specified, when referring to a polymer, the reference also applies to the oligomer. Accordingly, the terms polymer and oligomer are used interchangeably herein unless otherwise specified. Further, unless otherwise specified, the term “polymer” includes both homopolymers (ie, polymers that contain essentially one monomer) and / or copolymers (ie, polymers that contain two or more monomers).

  “Functional polymer” means a polymer and / or oligomer in contact with a functional group, optionally in contact with a catalyst, heat, initiator, or free radical source to cause the polymer to have a portion of the functional group or All incorporation, grafting, bonding, physical attachment, and / or chemical attachment occurs. Furthermore, a “functional component” is also defined to include a polymer polymerized directly from a monomer (or using an initiator having a functional group), where the polymer has a functional group at the chain end.

  “Functional oligomer” means an oligomer in contact with a functional group, optionally incorporating some or all of the functional group into the oligomer in contact with a catalyst, heat, initiator, or free radical source, Grafting, bonding, physical attachment, and / or chemical attachment occurs. Furthermore, a “functional oligomer” is also defined to include an oligomer that is directly oligomerized from a monomer (or using an initiator having a functional group), where the oligomer has a functional group at the chain end.

  “Functional group” means any compound having a weight average molecular weight of 1000 or less and having a carbon-carbon double bond, a carbon-carbon triple bond, and / or a heteroatom. Preferably, the functional group includes a heteroatom, where the heteroatom is B, N, O, Si, P, F, Cl, Br, I, S, or combinations thereof.

  Preferably, the functional group is a compound containing a heteroatom and unsaturation, such as maleic anhydride. Preferred functional groups are organic acids, organic amides, organic amines, organic esters, organic anhydrides, organic alcohols, organic acid halides (eg, acid chlorides, acid bromides, etc.), organic peroxides, and salts thereof. .

Polyolefin stereoregular olefin polymers and oligomers (“polyolefins” or “polyolefin polymers”) are generally, and in particular poly-α-olefin polymers comprising propylene or other C3 or higher α-olefin monomers are derived from the polymer backbone. Contains pendant hydrocarbyl groups. Pendant hydrocarbyl groups can be arranged in different stereochemical structures determined with respect to the polymer backbone. These configurations include atactic, isotactic, and / or syndiotactic structures.

  The degree and type of stereoregularity of the polyolefin polymer determines the physical properties of the composition containing such polymer. Other determinants of such compositions include monomer, comonomer, oligomer type and relative concentrations, polymer weight average molecular weight (Mw), polymer molecular weight distribution (MWD), polymer crystallinity, etc. May be included.

  Stereoregularity can be related to the crystallinity that an olefin polymer, particularly a poly-α-olefin polymer, can have. As used herein, the stereoregularity of the polymer reflects the stereochemical regularity of the hydrocarbyl group pendant to the polymer molecular backbone (ie, the polymer's stereoregularity).

  The four types of stereoregularity are expressed in poly-α-olefins as atactic, standard isotactic, isotactic stereoblock, and syndiotactic. All of these stereoregular configurations are shown primarily in the case of polypropylene, but theoretically, polymers of one or more C3 or higher α-olefins, cyclic olefins, and / or internal olefins as well, respectively. Is possible.

  Atactic poly-olefins are presumed that the hydrocarbyl groups are pendant to the polymer molecular backbone and are not in order with respect to the backbone. This random or atactic structure is represented by a polymer skeleton in which methylene and methine carbon are alternated, and side chains that are randomly substituted with methine carbon are oriented. The methine carbons randomly have R and S configurations, creating adjacent pairs of either similar configurations (“meso” or “m” dyads) or different configurations (“racemic” or “r” dyads). The atactic form of the polymer contains roughly the same proportions of meso and racemic dyads. Importantly, atactic poly-α-olefins, particularly atactic polypropylene, can be characterized by being soluble in aliphatic and aromatic solvents at room temperature. Since atactic polymers do not exhibit a regular order or repeat unit in the polymer chain, such atactic polymers can be said to be amorphous materials. As an amorphous material, atactic polymers tend to lack a molecular lattice structure and have almost no clear melting point. Thus, atactic poly-α-olefins are amorphous and usually do not have a measurable melting point and therefore exhibit little, if any, crystallinity.

Isotactic poly-olefins are characterized as having pendant hydrocarbyl groups lined with gaps on the same side or plane of the polymer backbone. As an example, using isotactic polypropylene, the isotactic structure usually has a pendant methyl group attached to the third carbon of a continuous monomer unit on the same side of the imaginary plane through the carbon backbone of the polymer. For example, all methyl groups are above or below the plane, as shown below.

  The degree of isotactic regularity can be measured by NMR techniques. The Bovey NMR nomenclature for isotactic pentads is. . . mmmm. . . Where each “m” represents a “meso” dyad or a continuous methyl group on the same side of the plane.

In isotactic poly-α-olefins, all monomer units have the same stereochemical configuration except for random errors and appear along the polymer. Such random errors are often seen as a single inversion of configuration and can be corrected in the immediately adjacent α-olefin monomer insertion to restore the original R or S configuration of the growing polymer chain. A single insertion of the inverted configuration yields rr triads, which distinguish between isotactic structures and the isotactic stereoblock forms shown below in NMR.

  This isotactic stereoblock form of poly-olefin may arise from a “site chirality exchange” and / or “chain end control” mechanism during the formation of the isotactic stereoblock poly-α-olefin polymer. The disorder or inversion of the chain structure decreases the isotacticity and thus allows the polymer to crystallize.

Syndiotactic poly-α-olefins are those in which hydrocarbyl groups are pendant to the polymer molecular backbone in turn, alternating from one side or plane to the opposite or plane with respect to the polymer backbone, as shown below.

  In NMR nomenclature, this pentad is. . . rrrr. . . Where each r represents a “racemic” dyad, ie, alternating methyl groups on both sides of the plane (JA Awen, “Catalytic Polymerization of Olefins”, (Ewen method); And edited by T. Keii, K. Soga; Kodanska Elsevier Pub; Tokyo, 1986, page 271). The proportion of r dyad in the chain determines the degree of syndiotacticity of the polymer and is related to the crystallinity of the polymer.

  The molecular chain skeleton of the syndiotactic polymer can be considered to be an olefin copolymer having an alternating stereochemical structure. A highly syndiotactic polymer is highly crystalline and can therefore have a distinct melting point similar to its isotactic polymorph, and can therefore be partially characterized by its melting temperature.

The amount or purity of stereoregularity in a polyolefin crystallinity polymer is related to the crystallinity of the polymer. Both isotactic and syndiotactic polyolefins can have varying levels of crystallinity. For purposes herein, the crystalline polyolefin has a crystallinity of 35% or higher, preferably about 50% or higher. As used herein, both high crystallinity “high” isotactic poly-α-olefins and syndiotactic poly-α-olefins are at least 35% by weight and are insoluble in xylene at room temperature. “High” crystallinity poly-α-olefins can also be at least partially characterized by a distinct melting temperature or temperature range. A “high” crystallinity “poly-α-olefin” can also be at least partially characterized by a crystallinity of 65% or higher, preferably 75% or higher.

  Contrary to crystalline polyolefins, amorphous poly-olefins have a crystallinity of less than about 35%. Intrinsically amorphous polyolefins, and in particular essentially amorphous poly-α-olefins (eg, essentially amorphous polypropylene) can be characterized as being essentially soluble in xylene, toluene at room temperature. Preferred essentially amorphous polyolefin polymers, copolymers, and / or oligomers, or blends thereof (collectively referred to as amorphous polyolefins) are preferably at least about 95% by weight, preferably based on the total weight of amorphous polyolefin present. Is at least about 96 wt.%, Preferably at least about 97 wt.%, Preferably at least about 98 wt.%, Preferably at least about 99 wt.%, Preferably at least about 99.5 wt. What is soluble. Amorphous polyolefins can also be characterized as having no or little discernable melting point or melting point range.

  The heat of fusion (Hf) can also be used to determine the crystallinity of the polymer according to the procedure described in ASTM E794-85. For example, a sample weighing about 7-10 mg is sealed in a sample pan. Differential scanning calorimetry data (DSC) is then recorded while the sample is first cooled to about −50 ° C. and then gradually heated to about 200 ° C. at a rate of about 10 ° C./min. The temperature is then maintained at about 200 ° C. for about 5 minutes before applying the second cooling-heating cycle. Both the first and second thermal experiments are recorded. The region below the melting peak can then be measured and used to measure heat of fusion and crystallinity. The crystallinity is preferably calculated using the formula [area under the curve (J / g) / B (J / g)] * 100, where B is the homology of the main monomer component in the sample. It is the heat of fusion of the polymer. These B values can be obtained, for example, from Polymer Handbook (Polymer Handbook), 4th edition, published by John Wiley and Sons, New York, 1999. By convention, if the polymer exhibits multiple melting or crystallization peaks, the total area below each peak was used to calculate crystallinity.

Amorphous syndiotactic rich polyolefin syndiotactic rich polyolefin polymer (srPP) may contain at least about 50% r dyad, as measured according to the Ewen method. In a preferred embodiment, the srPP comprises at least about 55% r dyad, preferably at least about 60% r dyad, preferably at least about 65% r dyad, preferably at least about 70% r dyad, preferably at least about 75. % R dyads, more preferably less than about 80% r dyads can be included based on the total number of r and m dyads present in the polymer.

  Amorphous syndiotactic rich polyolefin polymers (a-srPP) can include syndiotactic rich polyolefin polymers, essentially all of which are soluble in hexane, cyclohexane, toluene or xylene at room temperature. is there.

  Amorphous syndiotactic rich polyolefin polymer (a-srPP) can contain from about 50% rdyad to about 80% rdyad based on the total number of dyads present in the polymer. In a preferred embodiment, the amorphous srPP is about 55% r dyad to about 75% r dyad, preferably about 60% r dyad to about 75% r dyad, preferably about 60% r dyad to about 70%. From about 65% r dyad to about 70% r dyad, based on the total number of r dyads present in the polymer.

  Amorphous syndiotactic rich polyolefin polymer (a-srPP) can contain from about 6.25% to about 31.6% r pentad based on the total number of r pentads present in the polymer. In a preferred embodiment, the amorphous srPP comprises about 9.15% r pentad to about 31.6% r pentad, preferably about 13.0% r pentad to about 31.6% r pentad, preferably about Based on the total number of r pentads present in the polymer, from 13.0% r pentad to about 24.0% e pentad, preferably from about 17.9% r pentad to about 24.0% r pentad. Can be included.

  In a preferred embodiment, the amorphous syndiotactic rich polyolefin polymer is amorphous syndiotactic rich polypropylene (a-srPPr). The a-srPPr preferably has a weight average molecular weight (Mw) of 5,000,000 or less, a number average molecular weight (Mn) of about 3,000,000 or less, and a z-average molecular weight (Mz) of about 10,000,000 or less. The g ′ index is 1.5 or less, measured by weight average molecular weight (Mw) of the polymer using isotactic polypropylene as a reference, all of which can be measured by size exclusion chromatography, eg 3D SED, also referred to herein as GPC-3D.

  In a preferred embodiment, the a-srPPr of the present invention has an Mw of about 5,000 to about 5,000,000 g / mol, more preferably an Mw of about 10,000 to about 1,000,000, more preferably an Mw of about About 20,000 to about 500,000, more preferably Mw is about 50,000 to about 300,000, where Mw is measured as described herein.

  In a preferred embodiment, the a-srPPr of the present invention has an Mn of about 5,000 to about 3,000,000 g / mol, more preferably an Mn of about 10,000 to about 1,000,000, more preferably an Mn. About 30,000 to about 500,000, more preferably Mn is about 50,000 to about 200,000, where Mn is measured as described herein.

  In a preferred embodiment, the a-srPPr of the present invention has an Mz of about 10,000 to about 10,000,000 g / mole, more preferably an Mz of about 50,000 to about 1,000,000, more preferably an Mz of About 80,000 to about 500,000, more preferably Mz is about 100,000 to about 300,000, where Mw is measured as described herein.

  In a preferred embodiment, the a-srPPr of the present invention has a g ′ index value of from about 1 to about 1.5, more preferably g ′, as measured by the Mw of the polymer using the intrinsic viscosity of isotactic polypropylene as a reference. Is about 1.25 to about 1.45, g ′ is unambiguous and is measured as described herein.

  In a preferred embodiment, the a-srPPr of the present invention has a crystallization temperature (Tc) measured with a differential scanning calorimeter (DSC) of about 200 ° C. or lower, more preferably 150 ° C. or lower, more preferably discernable crystallization. There is no temperature.

  In a preferred embodiment, the a-srPPr of the present invention has a density of about 0.85 to about 0.95 g / ml at room temperature, more preferably about 0.87 to 0.00, as measured according to ASTM D-1505 test method. 92 g / ml, more preferably about 0.88 to about 0.91 g / ml.

  In a preferred embodiment, the a-srPPr of the present invention has a melt flow rate (MFR) inversely proportional to the weight average molecular weight Mw, measured according to the ASTM D-1238 (190c, 2.16 kg) test method, of 0.2 g / 10 minutes or more, preferably 2 to 500 g / 10 minutes, and more preferably 20 to 200 g / 10 minutes.

  Amorphous syndiotactic rich polyolefins can contain alpha olefins in the base polymer, and therefore amorphous syndiotactic rich polyolefins can contain about 50 wt% or more of C3-C20 alpha olefins, preferably about 50 wt%. % C3-C12α olefin, and more preferably about 50% or more by weight of C3-C10α olefin.

  Preferably, the amorphous syndiotactic rich polyolefin is about 60 wt% or more of propylene, preferably about 70 wt% or more of propylene, preferably about 80 wt% or more of propylene, preferably about 90 wt% or more of propylene. Preferably about 95% by weight or more of propylene, preferably about 99% by weight or more of propylene, based on the total weight of the polymer.

  The amorphous syndiotactic rich polyolefin of the present invention further comprises about 0.5 wt.% Or more ethylene, preferably about 1 wt.% Or more, preferably about 2 wt.% Or more, preferably about 3 wt.%. % Or more of ethylene, preferably about 4% by weight or more, preferably about 5% or more by weight of ethylene, based on the total weight of the polymer.

  For example, a-srPPr, with at least about 50% by weight propylene (C3) as the base polymer, ethylene (C2) and C4 to C20 alpha olefins, preferably C4 to C20 alpha olefins, more preferably C4 to C12 alpha olefins. Olefins can be included, more preferably C2 and C4 to C10 alpha olefins.

  Examples of preferred α-olefins include butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, undecene-1, dodecene-1, tridecene-1, pentodecene- 1, hexadecene-1, heptadecene-1, octadecene-1, and branched olefins such as 3-methylbutene-1, 4-methylpentene-1, and 4,4-dimethylpentene-1.

  The amount of alpha olefin in addition to the base polymer, when present in a-srPP, is about 0.001 wt% or more, based on the total weight of the polymer. Preferably, the amount of alpha olefin is about 0.1 wt% or more, more preferably about 1 wt% or more. Other alpha olefins can also be present in the base polymer at up to about 50% by weight. Preferably, the amount of other alpha olefins is about 20 wt% or less, more preferably about 10 wt% or less.

  In a preferred embodiment, essentially all a-srPP of the present invention (preferably a-srPPr) is essentially amorphous so that essentially all a-srPP is hexane, cyclohexane, xylene or toluene at room temperature. Means soluble. As used herein, essentially all a-srPP is at least about 95%, preferably at least about 96%, preferably at least about 97%, preferably, based on the total weight of a-srPP present. Is at least about 98 wt.%, Preferably at least about 99 wt.%, Preferably at least about 99.5 wt.% A-srPP is soluble in hexane, cyclohexane, xylene, or toluene at room temperature (ie, 25 ° C.) It means that.

  In a preferred embodiment, the a-srPP of the present invention, more preferably a-srPPr, has a heat of fusion (Hf) measured according to the procedure described in ASTM E794-85 of about 10 J / g or less, preferably about 9 J / g. Or less, preferably about 8 J / g or less, preferably about 7 J / g or less, preferably about 6 J / g or less, preferably about 5 J / g or less, preferably about 4 J / g or less, preferably about 3 J / g or less, Preferably it is about 2 J / g or less, preferably about 1 J / g or less, more preferably the heat of fusion cannot be detected according to the procedure described in ASTM E794-85.

  In a preferred embodiment, the a-srPP of the present invention, more preferably a-srPPr, has an ash content, measured according to the procedure described in ASTM D5630, of less than about 1% by weight, based on the total amount of polymer present, and more Preferably about 0.9 wt% or less, more preferably about 0.8 wt% or less, more preferably about 0.7 wt%, more preferably about 0.6 wt% or less, more preferably about 0.5 wt%. % Or less, more preferably about 0.4% by weight or less, more preferably about 0.3% by weight or less, more preferably about 0.2% by weight or less, more preferably about 0.1% by weight or less, more preferably About 0.05 wt% or less, more preferably about 0.01 wt% or less, more preferably about 0.005 wt% or less, measured according to ASTM D-5630, about 0.001 wt% The following ash content is more preferred.

Preparation of Amorphous Syndiotactic Rich Polyolefin Polymer Catalysts that can produce amorphous syndiotactic rich polyolefins, particularly amorphous syndiotactic rich polypropylene, are described in US Pat. No. 5,476,914, No. 6, 184, 326, 6,245,870, 5,373,059, 5,374,685 and 5,326,824. US Pat. Nos. 3,305,538 and 3,258,455 (Natta et al.), US Pat. No. 4,892,851 (Ewen et al.), US Pat. No. 5,270,410 (Job), US Pat. No. 5,340,917 (Eckman, et al.), US Pat. No. 5,476,914 (Ewen, et al.) Is quoted here in its entirety.

  In addition to catalyst selection, the reactant concentration and reaction pressure used to prepare the amorphous syndiotactic rich polyolefins of the present invention are also important. The reaction temperature is preferably controlled within about 10 ° C. relative to the set point, more preferably within about 9 ° C., more preferably within about 8 ° C., more preferably within about 7 ° C., more preferably within about 6 ° C. More preferably, it is within about 5 ° C, more preferably within about 4 ° C, more preferably within about 3 ° C, and even more preferably within about 2 ° C.

  Polymers prepared using a metallocene catalyst system and using the method disclosed in US Pat. No. 5,476,914 are preferred. Compared to other methods, a-srPPr prepared using a metallocene catalyst has a narrower molecular weight distribution and / or uniform comonomer distribution when compared to polymers produced using other catalysts such as, for example, vanadium catalysts. Other catalysts such as vanadium catalysts tend to yield polymers with higher ash content compared to those of the present invention. Thus, metallocene-generated a-srPP may have superior physical and mechanical properties and excellent processability compared to other a-srPPs. The most preferred type of a-srPP polymer is a metallocene catalyzed copolymer of propylene and ethylene or butene-1 with an ethylene or butene-1 comonomer content in the range of about 2-20% by weight.

  In general, a-srPP can be produced in a liquid-filled, single-stage reactor, such as di (p-triethylsilylphenyl) methylene (cyclopentadienyl) (3,8-di-t-butylfluorenyl). ) Zirconium dichloride, di (p-triethylsilylphenyl) methylene (cyclopentadienyl) (3,8-di-t-butylfluorenyl) hafnium dichloride, di (p-triethylsilylphenyl) methylene (cyclopentadienyl) ) 3,8-di-t-butylfluorenyl) zirconium dimethyl, di (p-triethylsilylphenyl) methylene (cyclopentadienyl) (3,8-di-t-butylfluorenyl) hafnium dimethyl, di (P-Triethylsilylphenyl) methylene (cyclopentadienyl) (3,3,6,6,9,9,12 12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl [b, h] fluorenyl) zirconium dichloride, di (p-triethylsilylphenyl) methylene (cyclopentadienyl) ( 3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl [b, h] fluorenyl) hafnium dichloride, di ( p-triethylsilylphenyl) methylene (cyclopentadienyl) (3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydro Dibenzyl [b, h] fluorenyl) zirconium dimethyl and di (p-triethylsilylphenyl) methylene (cyclopentadienyl) (3,3,6,6,9,9,12,12 Octamethyl -4,4,5,5,8,8,9,9- octahydro dibenzyl [b, h] fluorenyl) a continuous reactor using a suitable catalyst such as hafnium dimethyl.

  The catalyst can be activated (pre-activated) using a suitable activator (co-catalyst), for example, alumoxane compounds, modified alumoxane compounds, and ionized anion precursor compounds, where the ionized anion precursor compound is 1 Reactive sigma bond, pulling out metal ligand to form metal complex cation, giving charge equilibrium non-coordinating or weakly coordinating anion, for example, methylalumoxane (MAO) and N, N-dimethylanilinium tetrakis (Pentafluorophenyl) borate. Other preferred activators are described in paragraphs [00121] to [00151] of WO 2004/026921. Particularly preferred activators include those described in WO 2004/026921 at pages 77-78, paragraph [00135].

  The catalysts and catalyst systems described above are preferably used in solution, bulk, gas or slurry polymerization processes or combinations thereof, with liquid phase or bulk phase polymerization processes being preferred.

  In one embodiment, the present invention provides a solution, bulk, slurry or gas for the polymerization of one or more monomers having 3 to 30 carbon atoms, preferably 3 to 12 carbon atoms, and more preferably 3 to 8 carbon atoms. The purpose is a phase polymerization reaction. Preferred monomers are 1 of propylene, butene-1, pentene-1, 4-methyl-pentene-1, hexene-1, octene-1, decene-1, 3-methyl-pentene-1 and cyclic olefins or combinations thereof. Including the above. Other monomers can include vinyl monomers, diolefins such as dienes, polyenes, norbornene, norbornadiene, vinyl norbornene, ethylidene norbornene monomers. Preferably, a homopolymer or copolymer of propylene is produced. In other embodiments, both a homopolymer of propylene and a copolymer of propylene and one or more monomers as described above are produced.

  One or more reactors in parallel or in series can be used in the present invention. The catalyst component and activator can be sent as a solution or slurry and can be activated in series and sent separately to the reactor immediately before being sent to the reactor, or pre-activated to the reactor as an activated solution or slurry. You may send it in. A preferred operation is to activate the two solutions in series. See US Pat. No. 6,399,722 and WO0130862A1 for further information on how to introduce multiple catalysts into the reactor. Although these documents focus on gas phase reactors, the described techniques are equally applicable to other types of reactors such as continuous stirred tank reactors and slurry loop reactors. Polymerization can be a single reactor operation in which monomers, comonomers, catalysts / activators, scavengers and optional modifiers are continuously added to a single reactor, or each of two or more reactions with a series of the above components connected. In continuous reactor operation added to the reactor. The catalyst component can be added to the first series of reactors. Also, the catalyst component can be added to both reactors, one component added to the first reaction and the other component added to the other reactor.

  In one embodiment, 500 ppm or less of hydrogen can be added to the polymerization, or 400 ppm or less, or 300 ppm or less. In other embodiments, at least 50 ppm of hydrogen is added to the polymerization, or greater than 100 ppm, or greater than 150 ppm.

Functional Amorphous Syndiotactic Rich Polyolefin The present invention can include a contact product of the above-mentioned amorphous syndiotactic rich polyolefin, functional group, and functionalized catalyst, and the functional amorphous syndiotactic rich Resulting in a polyolefin rich in. Preferably, the amorphous syndiotactic rich polyolefin is amorphous syndiotactic rich polypropylene, the functional group is maleic anhydride, the functionalization catalyst is an organic compound oxide and functional with maleic anhydride. This results in a contact product containing polypropylene enriched in synthesized amorphous syndiotactic.

  Thus, the present invention can include polyolefins that are rich in the above-mentioned amorphous syndiotactic that are further functionalized with one or more other components to impart one or more functionalities to the polyolefin. The functionalized amorphous syndiotactic rich polyolefin is preferably an amorphous syndiotactic rich polypropylene, which is functionalized with maleic anhydride. Accordingly, amorphous syndiotactic rich polyolefins can contain unsaturated compounds (eg, compounds containing carbon-carbon double bonds, carbon-carbon triple bonds, and / or compounds containing heteroatoms (eg, B, N, O , Si, P, halogen (eg, F, Cl, Br, I), and / or S)). Functional groups include aromatic compounds, vinyl compounds, organic acids, organic amides, organic amines, organic esters, organic diesters, organic imides, organic anhydrides, organic alcohols, organic acid halides, organic peroxides, and / or salts. Or derivatives thereof.

  For simplicity of reference, unless otherwise specified, unsaturated compounds and / or compounds containing heteroatoms are collectively referred to herein as “functional groups, (abbreviations, FG)”. Functionalization (or grafting) means that one or more functional groups are incorporated into the amorphous syndiotactic rich polyolefin (a-srPP) of the present invention, grafted, bonded, physically and / or chemically. It is meant to produce polyolefins rich in amorphous syndiotactic attached and functionalized with functional groups (abbreviated “a-srPP-g-FG”, where “-g-FG” is a graft Functional group). The functionalization of the polyolefin preferably takes place on the polymer backbone, but may also take place at the polymer end and part of the polymer pendant to the polymer backbone. Functionalization can also occur with other functional groups and between various polymer chains.

  In a preferred embodiment, the functional syndiotactic rich polyolefin is essentially amorphous and essentially all a-srPP-g-FG of the present invention is in hexane, cyclohexane, xylene, or toluene at room temperature. It is soluble. As such, the a-srPP-g-FG is at least about 95 wt%, preferably at least about 96 wt%, preferably at least about 97 wt%, based on the total weight of a-srPP-g-FG present. %, Preferably at least about 98% by weight, preferably at least about 99% by weight, preferably at least about 99.5% by weight, is soluble in hexane, cyclohexane, xylene, or toluene at room temperature.

  In a typical embodiment, the functional group (ie, the compound that contains the functional group) utilizes radical copolymerization to provide amorphous syndiotactic rich polypropylene (a-srPPr), as described in detail herein. Can be grafted onto and may include the use of free radical initiators. This method is referred to herein as graft copolymerization. The result is a blend of propylene polymer or functional polymer rich in functionalized amorphous syndiotactic. Accordingly, the present invention includes the result of contacting a polyolefin, preferably an amorphous syndiotactic rich polyolefin, with a functional group in the presence of a free radical initiator.

  Preferred examples of functional groups include unsaturated carboxylic acids and salts thereof as well as acid derivatives such as, but not limited to, maleic anhydride, citraconic anhydride, 2-methylmaleic anhydride, 2-chloromaleic anhydride, anhydrous 2 , 3-dimethylmaleic acid, bicyclo [2,2,1] -5-heptene-2,3-dicarboxylic anhydride, and 4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, acrylic acid, Methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, crotonic acid, bicyclo (2.2.2) oct-5-ene-2,3-dicarboxylic acid anhydride, 1,2,3 4,5, & g, lo-octahydronaphthalene-2,3-dicarboxylic anhydride, 2-oxa-1,3-diketospiro (4.4) non-7-ene, bicyclo (2 2.1) Hept-5-ene-2,3-dicarboxylic acid anhydride, maleopimaric acid, tetrahydrophthalic acid anhydride, norborn-5-ene-2,3-dicarboxylic acid anhydride, nadonic acid anhydride Product, methyl nadic anhydride, anhydrous hymic acid, anhydrous methyl hymic acid, and / or x-methyl-bicyclo (2.2.1) hept-5-ene-2,3-dicarboxylic anhydride (XMNA) Can be mentioned.

  Examples of carboxylic acid esters include unsaturated carboxylic acid esters, such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate.

  The hydrolyzable unsaturated silane compound can contain a radically polymerizable unsaturated group and an alkoxylyl group or a silyl group in the molecule, and therefore the compound is a hydrolyzable silyl group and / or alkylene bonded to a vinyl group. A compound having a hydrolyzable silyl group bonded to a vinyl group by a group and / or a hydrolyzable silyl group bonded to an ester or amide such as acrylic acid or methacrylic acid. Examples of these include vinyltrichlorosilane, vinyltris (beta-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane monovinylsilane and monoallylsilane.

  Examples of unsaturated halogenated hydrocarbons include vinyl chloride and vinylidene chloride.

  Preferable examples of the radical initiator used for graft copolymerization include organic peroxides such as benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, t-butyl peroxyisopropyl carbonate, di-ti-butyl perphthalate, 2 , 5-Dimethyl-2,5-di (t-butylperoxy) hexene (Lupersol 101, ElfAtochem), 2,5-dimethyl-2,5-di (t-butylperoxy) hexene-3, di-t-butyl And peroxide, cumene hydroperoxide, t-butyl hydroperoxide, dilauryl peroxide and dicumyl peroxide.

  In a preferred embodiment, a-srPP can be grafted with maleic anhydride (MA) to produce a polypropylene rich in functional amorphous syndiotactic grafted with maleic anhydride (a-srPPr-g-MA); Here, maleic anhydride can be covalently bonded to any of the polymer chains contained in a-srPPr. Anhydrides functionally grafted onto the polymer can be maintained as anhydrides, can be oxidized into acid and / or aldehyde functional groups, and / or further reacted by methods known in the art to provide amides, amines, esters, acids. Other derivatives of functional groups such as salts can be introduced.

  In a preferred embodiment, the functional groups are present in the functional polymer (eg, a-srPP-g-FG) at about 0.005-99 wt%, based on the total weight of functional polyolefin present. In a preferred embodiment, the functional groups are about 0.01-99% by weight, preferably 0.05-90% by weight, preferably 0.1-75% by weight, based on the total weight of functional polyolefin or blend thereof present. %, More preferably 0.5-60 wt%, more preferably 0.5-50 wt%, more preferably 0.5-40 wt%, more preferably 0.5-30 wt%, more preferably 0 0.5 to 20 wt%, more preferably 0.5 to 15 wt%, more preferably 0.5 to 10 wt%, more preferably 0.5 to 5 wt%, more preferably 0.5 to 3 wt% More preferably 0.5 to 2% by weight, more preferably 0.5 to 1% by weight.

  In a further preferred embodiment, the functional amorphous polyolefin is a polypropylene rich in amorphous syndiotactic grafted with maleic anhydride (a-srPPr-g-MA). In a further preferred embodiment, the functional maleic anhydride is present in the amorphous syndiotactic rich polypropylene present, based on the total weight of the functional amorphous syndiotactic rich polypropylene or blend thereof. As measured, the concentration is about 0.005 to 10% by weight MA, more preferably 0.01 to 10% by weight MA, more preferably 0.5 to 10% by weight MA, more preferably 0.5 to 5% by weight MA. Present in a polymer or polymer blend comprising more preferably 1 to 5 wt% MA, more preferably 1 to 2 wt% MA, more preferably 1 to 1.5 wt% MA.

  Functional Amorphous Syndiotactic Rich Polyolefins of the Present Invention (a-srPP-g-FG), preferably maleic anhydride functionalized amorphous syndiotactic rich polypropylene (a-srPPr-g- MA) may comprise at least about 50% r dyad and less than about 80% r dyad, as measured according to the Ewen method. In a preferred embodiment, the a-srPPr-g-MA is based on the total number of r and m dyads present in the polymer, preferably at least about 55% dyad, preferably at least about 60% r dyad, preferably at least It can comprise about 65% r dyad, preferably at least about 70% r dyad, preferably at least about 75% r dyad, more preferably less than about 80% r dyad.

  Polyolefin polymer rich in functional amorphous syndiotactic (a-srPP-g-FG), preferably amorphous syndiotactic rich polypropylene functionalized with maleic anhydride (a-srPPr-g-MA) Can include from about 6.25% to about 31.6% r pentad based on the total number of r pentads present in the polymer. In a preferred embodiment, the a-srPP-g-FG is about 9.15% pentad to about 31.6% r pentad, preferably about 13 based on the total number of r pentads present in the polymer. 0.0% r pentad to about 31.6% r pentad, preferably about 13.0% r pentad to about 24.0% r pentad, preferably about 17.9% r pentad to about 24.0. % R pentad.

  In a preferred embodiment, the functionalized amorphous syndiotactic rich polyolefin polymer is a functional amorphous syndiotactic rich polypropylene (a-srPPr-g-FG), preferably functionalized with maleic anhydride. Polypropylene rich in amorphous syndiotactic (a-srPPr-g-MA). A-srPPr-g-FG, preferably a polypropylene rich in amorphous syndiotactic functionalized with maleic anhydride (a-srPPr-g-MA), preferably has a weight average molecular weight (Mw) of 5,000,000. 000 or less, preferably about 500 to about 5,000,000, number average molecular weight (Mn) is about 3,000,000 or less, preferably about 5000 to about 3,000,000, and z-average molecular weight (Mz) Is about 10,000,000 or less, preferably about 5000 to about 10,000,000, all of which can be measured by size exclusion chromatography, such as 3D SEC (also referred to as GPC-3D).

  In a preferred embodiment, the a-srPPr-g-FG of the present invention, preferably an amorphous syndiotactic rich polypropylene functionalized with maleic anhydride (a-srPPr-g-MA), has an Mw of about 5 1,000 to about 1,000,000 g / mol, more preferably about 10,000 to about 500,000, more preferably about 20,000 to about 300,000, more preferably about 50, Mw. 000 to about 200,000, and Mw is measured as described herein.

  In a preferred embodiment, the a-srPPr-g-FG of the present invention, preferably an amorphous syndiotactic rich polypropylene functionalized with maleic anhydride (a-srPPr-g-MA), has an Mn of about 2 1,000 to about 500,000 g / mol, more preferably about 5,000 to about 300,000, more preferably about 10,000 to about 200,000, more preferably about 20,000 to Mn. About 150,000, where Mn is measured as described herein.

  In a preferred embodiment, the a-srPPr-g-FG of the present invention, preferably an amorphous syndiotactic rich polypropylene functionalized with maleic anhydride (a-srPPr-g-MA) has an Mz of about 10 000 to about 10,000,000 g / mol, more preferably Mz is about 20,000 to about 1,000,000, more preferably Mz is about 40,000 to about 500,000, more preferably Mz is about 100,000 to about 400,000, where Mz is measured as described herein.

  In a preferred embodiment, the a-srPPr-g-FG of the present invention, preferably an amorphous syndiotactic rich polypropylene functionalized with maleic anhydride (a-srPPr-g-MA) is a differential scanning calorimeter. The crystallization temperature (Tc) measured by (DSC) is about 120 ° C. or lower, more preferably 100 ° C. or lower, and more preferably there is no discernable crystallization temperature.

  In a preferred embodiment, the a-srPPr-g-FG of the present invention, preferably an amorphous syndiotactic rich polypropylene functionalized with maleic anhydride (a-srPPr-g-MA) has a weight average molecular weight Mw Melt flow rate (MFR) inversely proportional to 0.2 g / 10 min, preferably 2-500 g / 10 min, and more preferably, as measured according to ASTM D-1238 (190c, 2.16 kg) test method 20-200 g / 10 min.

  a-srPPr-g-FG amorphous syndiotactic rich polyolefin, preferably maleic anhydride functionalized amorphous syndiotactic rich polypropylene (a-srPPr-g-MA) May contain an alpha olefin. For example, a-srPPr-g-FG contains propylene (C3) as a base polymer, ethylene (C2) and C4-C40 α-olefin, preferably C4-C20 α-olefin, more preferably C4-C12 α-olefin. Even more preferred are C2 and C4-C10 alpha olefins.

  Examples of preferred α-olefins include butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, undecene-1, dodecene-1, tridecene-1, pentodecene- 1, hexadecene-1, heptadecene-1, octadecene-1, and branched olefins such as 3-methylbutene-1, 4-methylpentene-1, and 4,4-dimethylpentene-1.

  The amount of alpha olefin in addition to the base polymer is present in a-srPPr-g-FG, preferably amorphous syndiotactic rich polypropylene (a-srPPr-g-MA) functionalized with maleic anhydride If it is, it is about 0.001% by weight or more based on the total weight of the polymer. Preferably, the amount of alpha olefin is about 0.1 wt% or more, more preferably about 1 wt% or more. Other alpha olefins can also be present in the base polymer at up to about 50% by weight. Preferably, the amount of other alpha olefins is about 20 wt% or less, more preferably about 10 wt% or less.

  In preferred embodiments, the a-srPP-g-FG of the present invention, more preferably a-srPPr-g-FG, even more preferably maleic anhydride functionalized amorphous syndiotactic rich polypropylene (a -SrPPr-g-MA) has a heat of fusion (Hf) measured according to the procedure described in ASTM E794-85 of about 10 J / g or less, preferably about 9 J / g or less, preferably about 8 J / g or less, preferably Is about 7 J / g or less, preferably about 6 J / g or less, preferably about 5 J / g or less, preferably about 4 J / g or less, preferably about 3 J / g or less, preferably about 2 J / g or less, preferably about 1 J / g or less, more preferably the heat of fusion cannot be detected according to the procedure described in ASTM E794-85.

  In a preferred embodiment, the a-srPP of the present invention before being functionalized to a-srPP-g-FG, more preferably amorphous syndiotactic functionalized with a-srPPr, preferably maleic anhydride. The included polypropylene (a-srPPr-g-MA) has an ash content, measured according to the procedure described in ASTM D5630, of less than about 1% by weight, more preferably about 0.9% by weight, based on the total amount of polymer present. %, More preferably about 0.8% or less, more preferably about 0.7%, more preferably about 0.6% or less, more preferably about 0.5% or less, more preferably about 0.4 wt% or less, more preferably about 0.3 wt% or less, more preferably about 0.2 wt% or less, more preferably about 0.1 wt% or less, more preferably Or about 0.05% by weight or less, more preferably about 0.01% by weight or less, more preferably about 0.005% by weight or less, measured according to ASTM D-5630, about 0.001% by weight or less. The ash content of is more preferred.

  In a preferred embodiment, a functionalized amorphous syndiotactic rich polyolefin, preferably an amorphous syndiotactic rich polypropylene functionalized with maleic anhydride (a-srPPr-g-MA) is thermally stable. Yes, so that Gardner color (measured by ASTM D-1544-68) of a-srPP-g-FG heat aged (eg, retained) at 180 ° C. for 48 hours compared to Gardner color of the original composition This means that it does not change more than 7 Gardner units. Preferably, the Gardner color of the functional polymer or composition comprising the functional polymer is 6 after heating for 48 hours above the melting point and before heating (eg, before heat aging) compared to the first functional polymer. It does not change more than Gardner units, preferably it does not change more than 5, more preferably 4, more preferably 3, more preferably 2, even more preferably 1 Gardner units.

  In the case of polypropylene rich in amorphous syndiotactic functionalized with maleic anhydride (eg grafted) (a-srPPr-g-MA), the thermal stability with reduced free acid groups present in the composition is reduced. It has been discovered that this can occur. Thus, in a preferred embodiment, the amount of free acid groups present in the blend comprising a-srPPr-g-MA, or a-srPPr-g-MA is based on the total weight of a-srPPr-g-MA present. Based on less than about 1000 ppm, more preferably less than about 500 ppm, and even more preferably less than about 100 ppm.

  It has also been discovered that various phosphites can contribute to instability. Thus, in yet another preferred embodiment, a-srPP-g-FG, more preferably a-srPPr-gMA is essentially free of phosphite, ie phosphite is a-srPP-g -FG means more preferably 100 ppm or less based on the total weight of a-srPPr-gMA.

Functionalization of Amorphous Syndiotactic- Rich Polyolefins Functional polyolefins rich in functional amorphous syndiotactic of the present invention (a-srPP-g-FG), preferably amorphous syndiotactic functionalized with maleic anhydride Functionalization of the amorphous syndiotactic rich polyolefin (a-srPP) with a functional group (FG) to produce a polypropylene rich in (a-srPPr-g-MA) is functionalized. It is obtained by contacting the functional group with the polymer, preferably in the presence of a radical initiator. In a preferred embodiment, the composition is heated at, near, or above the decomposition temperature of the one or more radical initiators used.

  In some embodiments, there is no need to specifically limit the amount of functional groups used, so conventional conditions, such as those used to functionalize isotactic polypropylene, may be used as the functional amorphous syndiotactic of the present invention. It can be used to produce tic-rich polyolefins, preferably polypropylenes rich in amorphous syndiotactic functionalized with maleic anhydride (a-srPPr-g-MA). Because the efficiency of copolymerization is relatively high, the amount of functional groups may be small (ie, about 1% by weight or less based on the total weight of the functional polymer).

  The radical initiator is preferably used in a proportion of 0.00001 to 10% by weight based on the weight of the functional group. Where applicable, the heating temperature depends on whether the contact of the polymer, functional groups, and, if used, the radical initiator is in the presence of a solvent. The contact temperature is preferably about 0 ° C. or more and less than about 500 ° C., more preferably about 50 to 350 ° C. If the heating temperature is less than 50 ° C., the reaction is slow and therefore may be less efficient. Above 350 ° C, degradation of the polymer or other components can occur. Accordingly, the a-srPP, preferably a-srPPr, of the present invention can be functionalized with functional groups using a solvent-based functionalization process and / or using a solvent-based melt-based functionalization process.

  In a solvent-based process, the reaction can be carried out in solution using a-srPP, preferably a-srPPr, or a radically stable 2-20 carbon atom, aroma as a 0.1-50 wt% slurry. In the presence of an aromatic compound, a halogenated aromatic compound, and / or a halogenated hydrocarbon compound having an alkyl-substituted aromatic hydrocarbon.

  Importantly, the amorphous polyolefins of the present invention, more preferably polyolefins rich in amorphous syndiotactic, even more preferably polypropylenes rich in amorphous syndiotactic, contain cyclic hydrocarbons and / or 6-20 carbon elements. It has been found that it can be functionalized in aliphatic solvents containing hydrocarbons. Preferred aliphatic solvents include cyclohexane, hexane, and mixtures containing cyclohexane and / or hexane.

  Thus, this unexpected discovery can avoid the use of aromatic and / or halogenated solvents, and thus the present invention can be exploited to reduce environmental problems, particularly with respect to the use of aromatic and / or halogenated solvents. It can be suppressed in mass production. This discovery also provides for the direct use of the polymer solution from the functionalizing polymerization reactor, thus avoiding additional termination and / or re-dissolution steps, as will be described in more detail herein. Furthermore, this discovery has the advantage that it is possible to use a solvent having a boiling point lower than that of the aromatic solvent. By using a solvent having a boiling point lower than that of benzene, toluene, xylene or the like in functionalization, for example, solvent removal from a functional polymer at a lower temperature and / or higher pressure compared to a specific aromatic solvent. Promoted. Thus, low temperature removal results in less polymer degradation, more efficient solvent removal, and productivity by operating at low temperature and / or high pressure compared to the operating conditions required for solvent removal of aromatic solvents. And a low cost solvent removal result.

  The functionalization process using a melt-based functionalization process can be performed in an apparatus such as an extruder, mixer, etc., with little or no solvent present, preferably no solvent is present, and the apparatus is in contact. Sufficient physical contact can occur between the affecting high viscosity components, thus resulting in functionalization of the amorphous syndiotactic rich polyolefin. In a melt-based functionalization process, the functionalization reaction can be accomplished at a relatively high temperature compared to the same reaction of a solution or solvent-based functionalization process.

  Other methods of functionalizing the a-srPP, preferably a-srPPr of the present invention include, but are not limited to, in solution or slurry (ie, using a solvent or diluent), or in the melt or mixture (ie , Solvent-free), selective oxidation, ozonolysis, epoxidation and the like.

  In the present invention, functionalization (for example, graft polymerization) can be performed in an aqueous medium. In this case, one or more dispersants can be used. Examples of suitable dispersants include saponified polyvinyl acetate, modified celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, and compounds containing OH groups such as polyacrylic acid and polymethacrylic acid. Furthermore, compounds used in ordinary aqueous suspension polymerization can also be widely used.

  Aqueous functionalization can be performed by suspending the polymer, functional groups, water-insoluble radical initiator and / or dispersant in water and heating the mixture. Here, the ratio of water to all functional groups is preferably 1: 0.1 to 1: 200, more preferably 1: 1 to 1: 100. The heating temperature is such that the half-life of the radical initiator is preferably 0.1 to 100 hours, more preferably 0.2 to 10 hours, preferably 30 ° C to 200 ° C, more preferably 40 ° C to 150 ° C. is there. In the heating step, the mixture is preferably sufficiently stirred so as to be in a suspended state. In this way, the grafted polyolefin is obtained in the form of granules.

  The weight ratio of functional group to polyolefin or blend containing the functionalized polyolefin is preferably 1:01 to 1: 10000, and the weight ratio of radical initiator to functional group is 0.00001 to 0.1. is there.

As mentioned above, the presence of free acid groups and phosphites in the functionalized srPP affects the thermal stability of a-srPP-g-FG, especially a-srPPr-g-MA. The concentration of free acid groups and other groups that adversely affect the thermal stability of a-srPP-g-MA is reduced and / or controlled as follows:
1. Reaction control. Contacting the material at a temperature and for a time sufficient to ensure essentially complete reaction, and thus essentially complete consumption of the added functional groups (eg maleic anhydride) during the functionalization process;
2. After washing. Contacting the functional polymer with at least one solvent, water, dilute acid, dilute base, or combinations thereof after the functionalization reaction (eg, washing);
3. Master Badge. A functional polymer masterbatch is produced and / or processed to be essentially free of free acid groups and / or other groups. The masterbatch has the above maleic anhydride functional group concentration required for the final composition, and the masterbatch is sufficient to produce the desired level of a-srPP-FG, preferably a-srPPr-MA in the final blend. 3. blend in the final blend (also called “let down”); or Humidity control. The humidity (eg, water) level in the functional polymer is maintained at a level that maintains the anhydride functionality of the anhydride (eg, MA).

Solution functionalization utilizing an aliphatic solvent is a preferred functionalization method to improve the thermal stability of a-srPP, preferably a-srPPr-g-MA.

  For reaction in solution, a-srPP can be dissolved in a suitable solvent (eg, an aromatic solvent such as benzene, toluene, or xylene, or an aliphatic solvent such as hexane or cyclohexane). After the solution containing a-srPP is heated to the desired temperature (eg, about 60-150 ° C.), the free radical initiator and functional groups (eg, reactive amide and / or maleic anhydride) are initiated in the grafting process. Can be added for. After stirring for about 30 minutes to about 5 hours or more, the solution is precipitated in a second solvent such as acetone to separate the functional polymer from the non-reactive modifier. The filtered product is then dried under vacuum (eg, at 120 ° C.) to obtain the final functional amorphous polyolefin product.

Thus, in one embodiment, the functionalization process can include the following steps:
1) adding an olefin monomer (eg, propylene), catalyst, activator, etc. to the reactor in a mixture of hexane or aliphatic solvent;
2) catalyst solution polymerization step;
3) monomer removal step;
4) performing solvent removal and product drying to produce a polymer;
5) Redissolving the polymer in a non-aliphatic solvent (eg, benzene, toluene, or non-hydrocarbon solvent) for solution functionalization;
6) Solvent-based functionalization step; and 7) Solvent removal step used in solvent-based functionalization.

In a preferred embodiment, the functionalization process includes the following steps:
1) adding an olefin monomer (eg, propylene), catalyst, activator, etc. to the reactor in a mixture of hexane or aliphatic solvent;
2) catalyst solution polymerization step;
3) monomer removal step;
4) Solvent-based functionalization step; and 5) Separation of the functionalized polyolefin (eg, precipitation by solvent addition, temperature control, and / or solvent removal used in solvent-based functionalization). Such a preferable method can be realized by a continuous stirring tank or a sequential reaction tank.

Accordingly, the method of producing the functionalized amorphous syndiotactic rich polyolefin of the present invention can include the following steps:
1) adding an olefin monomer, a metallocene catalyst and an activator into the aliphatic solvent of the reactor;
2) A step of performing a catalyst solution polymerization of an olefin monomer in a reactor to produce a polyolefin rich in amorphous syndiotactic;
3) A step of removing the monomer to remove the unreacted olefin monomer;
4) Solvent-based functionalization step; in an aliphatic solvent used in the solution polymerization step, a polyolefin containing a rich amount of amorphous syndiotactic and a functional group in the presence of a free radical initiator, and a functional amorphous syndiotactic And contacting at a temperature and for a time sufficient to produce a polyolefin rich in; and optionally,
5) Precipitating a polyolefin rich in functional amorphous syndiotactic by adding a solvent such as acetone and / or by removing an aliphatic solvent.

  Functionalizing propylene-based homopolymers and copolymers in solution is desirable for best functional chemical control. Furthermore, in some applications it is desirable that the functional polymer can be transported in solution to the intended application, for example, a primer for a TPO bumper.

Melt functionalization involves a process similar to that of solutions, except that no solvent is required, the reaction takes place in a mixing device (eg, extruder, Brabender), and the temperature is higher than that of the solvent-based process. Is also expensive. Accordingly, the method of producing a functionalized amorphous syndiotactic rich polyolefin of the present invention can include the following steps:
A. Adding a melt comprising a polyolefin rich in amorphous syndiotactic, functional groups, and a free radical initiator to a mixing device; and B. Contacting the melt in a mixing device at a temperature and for a time sufficient to produce a polyolefin rich in functional amorphous syndiotactic.

In a preferred embodiment, the method can include the following steps:
A. Adding a melt comprising an amorphous syndiotactic rich polyolefin, maleic anhydride, and an organic peroxide as a free radical initiator to a mixing device; Contacting the melt in a mixing apparatus at a temperature and for a time sufficient to produce the a-srPP-g-MA of the present invention.

In a preferred embodiment, nanoclay can be added to the polymer and the method of producing a functionalized amorphous syndiotactic rich polyolefin can include the following steps:
A. Adding a melt comprising amorphous syndiotactic rich polyolefin, functional group, optional nanoclay, and free radical initiator to a mixing device;
B. Contacting the melt and any nanoclay in a mixing device at a temperature and for a time sufficient to produce a polyolefin rich in pre-functional amorphous syndiotactic, rich in amorphous syndiotactic The polyolefin comprises about 50% by weight or more of C ₃ -C ₄₀ α-olefin;
Contains about 50% to about 80% r dyad, based on the total number of r and m dyads present in the polyolefin; and has a heat of fusion of 10 J / g or less according to the procedure described in ASTM E794-85.

  Preferably, the method is such that the amorphous syndiotactic rich polyolefin further comprises an ash content of 1 wt% or less and / or the functional amorphous syndiotactic rich polyolefin is functionalized with maleic anhydride. A polyolefin rich in amorphous syndiotactic and / or further comprising an organoclay after the contacting step B.

Applications comprising the polymers of the invention Polyolefins rich in amorphous syndiotactic, preferably amorphous syndiotactic rich polypropylene and functional amorphous syndiotactic rich polyolefins, preferably functional amorphous syndiotactic Abundant polypropylene, more preferably, amorphous syndiotactic rich polypropylene functionalized with maleic anhydride can be used in a number of applications. Examples include injection molded parts, films, laminates, substrates, other products, and compatibilizers in the formation of various materials from recycled materials, pure substances or a mixture of both.

  The injection molded part includes various products produced by injection molding as known to those skilled in the art. Films include melt blown films, extruded films, cast films and the like. The laminate includes one or more layers, may or may not include additional adhesives, and / or includes other materials disposed between the laminate layers. The substrate is non-polar or polar and can be affected by the incorporation of functional groups within the polyolefins rich in functional amorphous syndiotactic of the present invention.

  The polymer of the present invention may comprise a masterbatch. In an embodiment, the masterbatch is a polyolefin rich in amorphous syndiotactic as described above, preferably a polypropylene rich in amorphous syndiotactic and / or a polyolefin rich in functional amorphous syndiotactic, preferably Can comprise a polypropylene rich in functional amorphous syndiotactic, more preferably a polypropylene rich in amorphous syndiotactic functionalized with maleic anhydride. The masterbatch can also include a variety of other additives and / or other components that are tailored to the end use, so that the materials in the masterbatch can be “let down” for a particular end use.

  Syndiotactic rich polyolefin, preferably amorphous syndiotactic rich polypropylene and functional amorphous syndiotactic rich polyolefin, preferably functional amorphous syndiotactic rich polypropylene, more preferably The amorphous properties of polypropylene rich in amorphous syndiotactic functionalized with maleic anhydride also allow the present invention to be used in liquid form and are preferably dissolved in a suitable solvent. As such, the present invention can be applied to the substrate by atomization and / or spraying by techniques known to those skilled in the art.

A polymer- rich amorphous syndiotactic rich polyolefin, preferably an amorphous syndiotactic rich polypropylene and a functional amorphous syndiotactic rich polyolefin, preferably a functional amorphous syndiotactic rich polypropylene, More preferably, an amorphous syndiotactic rich polypropylene functionalized with maleic anhydride can be utilized as a blend in combination with at least one, preferably one or more additives. The polymers of the present invention can therefore be used as additives, adhesives, or base polymers in adhesive blends. As used herein, an additive is any substance or combination thereof that promotes, improves, modifies or interferes with the physical properties of the polymer blend, or a polyolefin rich in amorphous syndiotactic of the present invention, preferably amorphous syndiotactic. Abundant polypropylene and / or functionalized amorphous syndiotactic rich polyolefin, preferably functional amorphous syndiotactic rich polypropylene, more preferably maleic anhydride functionalized amorphous syndiotactic It can be any material or combination thereof that aids in the use of abundant polypropylene.

  Additives suitable for use herein include one or more C2-C40 polymers, elastomers, random copolymers, impact copolymers, fractional polymers, tackifiers, crosslinking agents, antioxidants, neutralizing agents, nucleating agents Agents, fillers, adhesion promoters, oils, plasticizers, waxes, low molecular weight polymers, ester polymers and / or other additives can be included.

In the C2-C40 polymer 1 embodiment, the additive may comprise various C2-C40 polyolefin polymers ("polymers") alone or in blends with other polymers and / or additives. Thus, the additive can comprise a separate polymer alone or a blend of separate polymers. The blend can include two or more polyolefins, such as polypropylene-polyethylene copolymers, two or more polypropylene copolymers, wherein each component of the polymer blend is suitable alone as an additive.

  In a preferred embodiment, the additive comprises metallocene polyethylene (mPE's) and / or metallocene polypropylene (mPPr's). mPE and mPPr homopolymers or copolymers are usually produced in solution, slurry, high pressure or gas phase in combination with alumoxane and / or non-coordinating anions using mono- or bis-cyclopentadienyl transition metal catalysts. The The catalyst and activator may be supported or unsupported and the cyclopentadienyl ring may be substituted or unsubstituted. Some products produced using such catalyst / activator combinations are from ExxonMobil Chemical Company (Baytown, TX) under the trade names EXCEED®, ACHIEVE® and EXACT. It is marketed as (registered trademark). For further information on methods and catalysts / activators for producing such mPE homopolymers and copolymers, see WO 94/26816; WO 94/03506; EPA 277,003; EPA 277,004; US Pat. No. 5,153,157. U.S. Pat. No. 5,198,401; U.S. Pat. No. 5,240,894; U.S. Pat. No. 5,017,714; CA 1,268,753; U.S. Pat. No. 5,324,800; 368; U.S. Pat. No. 5,264,405, EPA 520,732; WO 92/00333; U.S. Pat. No. 5,096,867; U.S. Pat. No. 5,507,475; EPA 426 637; EPA 573 403; 732; EPA 495 375; EPA 500 944; EPA 570 82; WO91 / 09882 Patent; WO94 / 03506 Patent and U.S. Patent No. 5,055,438.

In other embodiments, the additive is homopolypropylene, propylene copolymerized with up to 50 wt% ethylene or C4-C20 alpha-olefin, isotactic polypropylene, highly isotactic polypropylene (eg, greater than about 50% ), Syndiotactic polypropylene, random copolymers of propylene and ethylene, and / or butene and / or hexene, 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 ) , Copolymers with high density polyethylene (density 0.945 to 0.98 g / cm ³ ), ethylene vinyl acetate, ethylene methyl acrylate, acrylic acid, polymethyl methacrylic acid or other polymers polymerizable by high pressure free radical processes; Polyvinyl chloride, polybutene-1, isotactic polybutene, ABS resin, elastomer, such as ethylene-propylene rubber (EPR), vulcanized EPR, EPDM, block copolymer elastomer, such as SBS, nylon (polyamide), polycarbonate, PET resin, Cross-linked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromatic monomers such as polystyrene, poly-1 esters, graft copolymers, usually polyacrylonitrile homopoly Including over or copolymers, thermoplastic polyamides, polyacetal, polyvinylidene fluoride and other fluorinated elastomers, polyethylene glycols and polyisobutylene.

  Other preferred propylene copolymers useful herein as additives are “second polymer component (SPC)” as US applications USSN 60 / 133,966 and 1999/6 filed concurrently on May 13, 1999. It is described in detail in USSN 60 / 342,854 filed on May 29, and in more detail as “propylene olefin copolymer” in USSN 90 / 346,460 filed July 1, 1999. Yes. These documents are hereby incorporated by reference in their entirety for purposes of US practice.

  In a preferred embodiment, the additive may comprise propylene, one or more comonomers (eg, ethylene, an α-olefin having 4 to 8 carbon atoms, and styrene) and optionally one or more α, ω dienes. The amount of diene is preferably about 10% by weight or less, more preferably about 5% by weight or less. Preferred dienes include those used for vulcanization of ethylene propylene rubber, preferably ethylidene norbornene, vinyl norbornene, dicyclopentadiene, and 1,4-hexadiene (commercially available from DuPont Chemicals).

  In one embodiment, the additive may comprise two or more polypropylene copolymers, preferably each having a different α-olefin content, one in the range of 7-13 mol% α-olefin and the other in the range of 14-22. It is within the range of mol% α-olefin. A preferred α-olefin is ethylene. The use of two polymer components is believed to provide a useful improvement in the tensile elongation properties of the final blend.

  Suitable polymers here as additives are C3-C40 homopolymers or copolymers rich in amorphous syndiotactic and / or C3-C40 homopolymers or copolymers rich in at least partly crystalline syndiotactic Including. An at least partially crystalline polyolefin is defined as a polyolefin homopolymer or copolymer having at least 10% by weight xylene or toluene solubility at room temperature. Preferably, the additive has a solubility in xylene or toluene at room temperature of 15% by weight, preferably 20% by weight, preferably 25% by weight, preferably 30% by weight, preferably 35% by weight, preferably 40% by weight. , Preferably 45% by weight, preferably 50% by weight, preferably 55% by weight, preferably 60% by weight, preferably 65% by weight, preferably 70% by weight, preferably 75% by weight, preferably 80% by weight, preferably Includes polyolefins rich in syndiotactic that are 85% by weight, preferably 90% by weight, preferably 95% by weight. More preferably, the additive syndiotactic rich polyolefin described above comprises at least partially crystalline syndiotactic rich polypropylene (srPPr).

  Polypropylene rich in at least partially crystalline syndiotactic (srPPr) can be defined herein as containing at least about 80% [r] dyad. Preferably at least about 85% [r] dyad, preferably at least about 90% [r] dyad, more preferably at least about 95% [r] dyad, and even more preferably at least about 99% [r] dyad.

  The additive also includes at least partly crystalline syndiotactic rich polyolefins including ethylene (C2) and other α-olefins including C4 to C40 α-olefins with polypropylene as the base polymer. Can do. Examples of α-olefins include butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, undecene-1, dodecene-1, tridecene-1, pentodecene- 1, hexadecene-1, heptadecene-1, octadecene-1, and branched olefins such as 3-methylbutene-1, 4-methylpentene-1, and 4,4-dimethylpentene-1.

  When present in polypropylene that is rich in at least partially crystalline syndiotactic, the amount of other α-olefins is greater than or equal to about 0.001% by weight, based on the total weight of the polymer. Preferably, the amount of the other α-olefin is about 0.1% by weight or more, more preferably about 1% by weight or more. Other α-olefins are also present in the base polymer at up to about 50% by weight. Preferably, the amount of other α-olefins is no more than about 20% by weight in the base polymer, more preferably about 10% by weight.

In other embodiments of the elastomer, the additive can include an elastomer. Examples of suitable elastomers include one or more polypropylene copolymers having elastic properties. Such preferred propylene copolymers having elastic properties can be prepared according to the procedures in WO 02/36651 cited herein. Similarly, the additive may comprise a polymer consistent with that described in WO03 / 040202, WO03 / 040095, WO03 / 040201, WO03 / 040233 and / or WO03 / 040442. In addition, the additives can also include polymers consistent with those described in EP 1,233,191 and US Pat. No. 6,525,157.

  Preferred propylene copolymers having elastic properties include those prepared by polymerizing C2 or C4 to C20 α-olefins with propylene, most preferably propylene and ethylene, chiral metallocene catalyst and activator and optionally Polymerizes in the presence of a scavenger. Comonomers used with propylene may be linear or branched. Preferred linear α-olefins include ethylene (C2) and C4-C8 α-olefins. Examples of preferred α-olefins include ethylene, 1-butene, 1-hexene and 1-octene, more preferably ethylene or 1-butene. Preferred branched chain α-olefins include 4-methyl-1-pentene, 3-methyl-1-pentene and 3,5,5-trimethyl-1-hexene.

  Preferred additives, including propylene copolymers having elastic properties, have an average propylene content of from about 68% to about 92%, more preferably from about 75% to about 91%, and even more preferably from about 78% to about 88% on a molar basis. Most preferably from about 80% to about 88%. The balance of the copolymer is one or more alpha-olefins as specified above, and optionally a small amount of one or more diene monomers. Preferably, the polypropylene copolymer has from about 8 to 32 mole% ethylene as a comonomer, more preferably from about 9 to about 25 mole% ethylene, even more preferably from about 12 to about 22 mole% ethylene, and most preferably from about 13 to In the range of 20 mol% ethylene.

  The use of chiral metallocene catalysts to produce these propylene copolymers with elastic properties ensures that the methyl groups of the propylene residues have mostly the same stereoregularity. Both syndiotactic and isotactic stereostructures of propylene are possible, and isotactic polymers are particularly preferred. The stereoregularity of the propylene residues results in polymer crystallinity. With respect to the additive polymer of the present invention, the low crystallization level of the polypropylene copolymer is derived from the isotactic polypropylene obtained by incorporation of the α-olefin comonomer described above.

Particularly preferred additives comprising propylene copolymers having elastic properties preferably include semi-crystalline propylene copolymers having the following characteristics:
1. 1. a heat of fusion of from about 0.5 J / g to about 25 J / g, more preferably from about 1 J / g to about 20 J / g, and most preferably from about 1 J / g to about 15 J / g; Crystallinity of about 0.25% to about 15%, more preferably about 0.5% to about 13%, and most preferably about 0.5% to about 11% (the crystallinity of the polypropylene copolymer is Expressed in terms of percent, the highest thermal energy of polypropylene is rated at 189 J / g for use herein, ie, for use herein, 100% crystallinity is assumed to be equal to 189 J / g); And / or 3. A single broad melting point or melting transition (a sample of polypropylene copolymer may show a peak adjacent to the second melting peak or the main peak, but for purposes herein, these are combined together as a single melting point or melting transition. 3); and / or A melting point of about 25 ° C to about 75 ° C, preferably in the range of about 25 ° C to about 68 ° C, more preferably in the range of about 30 ° C to about 60 ° C (the highest melting transition peak is considered as the melting point); and / or 5 . 5. A weight average molecular weight of 10,000 to 5,000,000 g / cc, preferably 80,000 to 500,000; and / or MWD (Mw / Mn) 1.5-40.0, more preferably about 1.8-5, and most preferably 1.8-3; and / or 7. Mooney viscosity ML (1 + 4) at 125 ° C Is less than 100, more preferably less than 75, even more preferably less than 60, and most preferably less than 30.

  Other elastomers suitable for use herein include all natural and synthetic rubbers, including those defined in ASTM D1566. In a preferred embodiment, the elastomer is a rubber reinforced composition. In a particularly preferred embodiment, the rubber reinforcing composition is a two (or more) phase system and the rubber is a discontinuous phase within a continuous phase comprising a polyolefin rich in functional amorphous syndiotactic. Examples of preferred elastomers include ethylene propylene rubber, ethylene propylene diene monomer rubber, neoprene rubber, styrenic block copolymer rubber (including SI, SIS, SB, SBS, SIBS, SEBS, SEPS, etc. (S is styrene, I is isoprene). , B is butadiene, EB is ethylene butylene, and EP is ethylene propylene)), butyl rubber, halobutyl rubber, copolymers of isobutylene and para-alkylstyrene, and halogenated copolymers of isobutylene and para-alkylstyrene.

Random copolymer In other embodiments, the additive may comprise a random copolymer. Random copolymers suitable for use herein can be produced by copolymerizing propylene and other monomers such as ethylene, butene and higher alpha-olefins, most commonly ethylene, in a single reactor process. The ethylene content of these additive copolymers is preferably in the range of 3-4 mol%, 14-17 mol% or less, preferably 1 mol% -20 mol%.

  Examples of suitable random copolymers also include randomly crystallizable propylene copolymers having a narrow composition distribution. The intramolecular composition distribution of the polymer can be determined by hot fractionation in a solvent such as a saturated hydrocarbon such as hexane or heptane. Having a narrow composition distribution means that about 75 wt.%, And more preferably 85 wt.% Of the polymer is isolated as a 1 or 2 adjacent soluble fraction from the remaining polymer in the immediate or previous fraction. To do. Thus, in copolymers having a narrow compositional distribution, each of these fractions is a composition having a difference in average ethylene content weight percent in the polypropylene copolymer of 20% or less (relatively) and more preferably 10% (relatively). Weight% ethylene content).

  The length and distribution of the stereoregular propylene sequence in the preferred random crystallizable polypropylene copolymer corresponds to a substantially random statistical copolymerization, the sequence length and distribution being related to the copolymerization reaction ratio. Substantially random means that the copolymer reaction ratio is usually 1 or less. In stereoblock structures, the average length of polypropylene sequences is longer than substantially random copolymers with similar composition, and stereoblock structures with polypropylene sequence distributions that match the bulk structure rather than a substantially random statistical distribution It is not similar to a polymer with The reaction ratio and sequence distribution of the polymer can be determined by 13C NMR, with ethylene residues located in relation to neighboring propylene residues. The crystallizable copolymer having the required randomness and narrow composition distribution suitable for use as an additive here is preferably for (1) a single site catalyst and (2) substantially all polymer chains of the preferred polypropylene copolymer. It is prepared using a well-mixed continuous flow stirred tank polymerization reactor that allows only a single polymerization environment.

Impact Copolymers In other embodiments, the additive can include one or more impact copolymers, which are also referred to as heterophase copolymers or block copolymers. An impact copolymer suitable for use herein can be defined as a blend of isotactic PP and an elastomer such as ethylene-propylene rubber. In a preferred embodiment, the impact copolymer blend is present in a two (or more) phase system, where the impact copolymer is a discontinuous phase in the adhesive composition and a-srPP-g-FG and / or other additions as described above. Things are a continuous phase.

Fractional polymers In other embodiments, the additive may comprise one or more polymers produced using so-called “fractional catalysts”. Such polymers are referred to herein as “fractional polymers” and include linear isotactic polymers having one or several C2-C20 olefin structures, in which the statistical distribution of stereo-mirror image errors in the polymer chain The isotacticity resulting from is in the range of [mmmm] pentad concentration of 25-60%. The determination of the pentad concentration is described in, for example, A. Ewen, “Catalytic Polymerization of Olefins” (Ewan method) and edited by T. W. et al. Keii, K .; Soda; Kodanska Elsevier Pub; Tokyo, 1986, p. 271, and can be measured using the following reference.

  Fractional polymers suitable for use as additives include those described in US Pat. No. 6,555,643, where it is essential to locate the stereo-mirror image error in the polymer chain itself so that a specific pentad concentration occurs. is there. Preferably, the fractional polymer comprises a [rmrm] pentad concentration having a maximum of 2.5% of the total pentad region where the [rmrm] pentad concentration is essentially zero (ie, completely missing).

  The mixed concentration of [rrrr] and [rrrm] pentads in a suitable fractional polymer is greater than the [rmrm] pentad concentration. In a preferred embodiment, the fractional polymer is a linear, isotactic polymer and has a weight average molecular weight of 100,000 to 800,000 g / mol, preferably 110,000 to 500,000 g / mol, and more preferably 120, 000 to 300,000 g / mol. The molecular weight distribution Mw / Mn of the polymer according to this preferred embodiment is about 1.2 to 3.5. Suitable fractional polymers have a glass transition temperature Tg of −50 ° C. to + 30 ° C., preferably −20 ° C. to + 10 ° C. as measured by DSC.

  Preferred fractional polymers include linear, isotactic polymers containing one or several C2-C20 olefins. Preferably, the olefin is C3-C20 alk-1-ene, such as propene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-octene, 1-nonene. 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene, and 1-eicosene or C5-C20 cycloolefins such as cyclopentene, cyclohexene, norbornadiene and derivatives thereof, with polypropylene being particularly preferred. Also preferred are copolymers prepared from propylene and C4-C20 olefins or cycloolefins.

  Preferred fractional polymers are essentially soluble in toluene at 20-80 ° C. In addition, such polymers exhibit a distinct elastic behavior in tensile strength tests and a distinct rubber-elastic stable state (plateau) compared to polymer flow action or failure (US Pat. No. 6,555,643). (See FIG. 1). Suitable fractional polymers also have a crystallization melting temperature measured by a “Differential Scanning Calorimeter” (DSC) in the range of −50 ° C. to 150 ° C. The elastic-thermoplastic behavior of suitable fractional polymers is state-of-the-art, i.e. distinctly different from the polymers disclosed, for example, in EP 0 707 016 A1.

Thus, fractional polymers include those produced utilizing a fractional catalyst having the general formula:

Where M is a metal selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium or tantalum; X is a halogen or a C1-C5 alkyl, aryl, or benzyl group, R ¹ , R ² , R ³ , R ⁴ , R ⁶ , and R ⁷ are linear or branched C1-C10 alkyl, C5-7 cycloalkyl, and in turn carry one or several C1-C6 alkyl residues as substituents Can be C6-C18 aryl, arylalkyl or alkylaryl, where R ¹ , R ² , R ³ , R ⁴ , and R ⁶ , R ⁷ repeat, but partially or simultaneously C ⁵ -C ⁷ cycloalkyl Or can be integrated into the fused aryl ring.

  In the case of a metallocene compound according to the above formula, the 7th indenyl carbon adjacent to the carbon substituted by residue R7 and the 4th indenyl carbon adjacent to the carbon substituted by residue R6 may be replaced only by hydrogen. Important, thereby providing a particularly advantageous catalyst for the preparation of isotactic elastomers according to the present invention. Suitable bridging structural units E are -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CR9R10-, SiR9R10-, or GeR9R10-, wherein R9 and R10 are C1-C8 alkyl, C4-7 cycloalkyl. Or aryl, and R9 and R10 can be joined together to form a ring structure.

The tackifier additive can also include a tackifier. Examples of suitable tackifiers include aliphatic hydrocarbon resins, aromatic modified aliphatic hydrocarbon resins, hydrogenated polycyclopentadiene resins, polycyclopentadiene resins, gum rosin, gum rosin ester, wood rosin, wood rosin ester, Tall oil rosin, tall oil rosin ester, polyterpene, aromatic modified polyterpene, terpene phenol resin, aromatic modified hydrogenated polycyclopentadiene resin, hydrogenated aliphatic resin, hydrogenated aliphatic aromatic resin, hydrogenated It is selected from the group consisting of terpenes and modified terpenes, hydrogenated rosin acids, and hydrogenated rosin esters. In some embodiments, the tackifier is hydrogenated.

  In other embodiments, the tackifier is non-polar, meaning that the tackifier is substantially free of monomers having polar groups. Preferably, polar groups are not present, but if present, are preferably not less than 5% by weight, preferably not less than 2% by weight, more preferably not more than 0.5% by weight. In some embodiments, the tackifier has a ring and ball softening point as measured by ASTM E-28 between 80 ° C and 150 ° C, preferably between 100 ° C and 130 ° C. In another embodiment, the resin is a liquid and has a ring and ball softening point of 10-70 ° C.

  The tackifier comprises about 1 to about 80% by weight, more preferably 2 to 40% by weight, and even more preferably 3 to 30% by weight, based on the weight of the adhesive composition.

Preferred additives include hydrocarbon resins used as tackifiers or modifiers, which include the following:
1. Resin such as C5 / C6 terpene resin, styrene terpene, α-methylstyrene terpene resin, C9 terpene resin, aromatic modified C5 / C6, aromatic modified cyclic resin, aromatic modified dicyclopentadiene base resin or a mixture thereof. Other preferred resins include those disclosed in WO 91/07472, US Pat. No. 5,571,867, US Pat. No. 5,171,793 and US Pat. No. 4,078,132. These resins are obtained from cationic polymerization of compositions containing one or more of the following monomers: C5 diolefins (eg, 1-3 pentadiene, isoprene, etc.); C5 olefins (eg, 2-methylbutene, cyclopentene, etc.); C6 Olefins (eg hexene), C9 vinyl aromatics (eg styrene, α-methylstyrene, vinyltoluene, indene, methylindene etc.); cyclic compounds (eg dicyclopentadiene, methyldicyclopentadiene etc.); and or terpenes (eg Limonene, Karen, Tuyon etc.).

  2. Resin obtained by thermal polymerization of dicyclopentadiene, and / or dimer or oligomer of cyclopentadiene and / or methylcyclopentadiene, and / or vinyl aromatic (for example, styrene, α-methylstyrene, vinyltoluene, indene, Resin obtained by thermal polymerization with methylindene or the like.

  The resin obtained after polymerization and separation of unreacted material can be hydrogenated if desired. Examples of preferred resins used as additives herein include US Pat. No. 4,078,132; WO 91/07472; US Pat. No. 4,994,516; EP0 046 344A; EP0 082 726A; No. 5,171,793.

Crosslinking agent In other embodiments, the additive may further comprise a crosslinking agent. Preferred crosslinkers are present on polypropylenes rich in amorphous syndiotactic grafted with functional groups present on a-srPP-g-FG, such as maleic anhydride (eg a-srPPr-g-MA) Including those having a functional group capable of reacting with an anhydride group. Preferred crosslinkers include alcohols, multiols, amines, diamines and / or triamines. Particular examples of crosslinking agents useful in the present invention include polyamines such as ethylenediamine, diethylenetriamine, hexamethylenediamine, diethylanilinopropylamine, and / or methanediamine.

Antioxidants In other embodiments, the additive can include one or more phenolic antioxidants. Preferred examples of phenolic antioxidants include substituted phenols, such as 2,6-di-t-butylphenol, wherein the hydrogen atoms at the 2 and / or 6 positions are substituted with alkyl residues. Examples of common phenolic antioxidants include 2,6-di-t-butyl-p-cresol, 2,4,6-tri-t-butylphenol, vitamin E, 2-t-butyl-6 (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,2'-methylene-bis (4-methyl-6-t-butylphenyl), 2,2 '-Methylene-bis (4-ethyl-6-tert-butyl-phenol), 2,2'-methylene-bis (6-cyclohexyl-4-methylphenol), 1,6-hexanediol-bis ([3- (3,5-di-t-butyl [4-hydroxyphenyl])] propionic acid and pentaerythrityl-tetrakis- [3- (3,5-di-t-butyl-4-hydroxyphenyl)] propionic acid Is mentioned . Preferred antioxidants include phenolic antioxidants, for example, a Irganox1010, Irganox 1076, both Ciba - commercially available from Geigy.

Neutralizing / Nucleating Agent The additive of the present invention comprises a neutralizing agent such as calcium stearate, magnesium hydroxide, aluminum hydroxide or hydrotalcite, and / or a nucleating agent such as benzoate, sodium-2, 2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, benzylsorbitol and the like can also be included.

In other embodiments of the filler, the additive can also include a filler. Suitable fillers include titanium dioxide, calcium carbonate, barium sulfate, silica, silicon dioxide, carbon black, sand, glass beads, mineral aggregate, talc, clay and the like.

  In another embodiment, it is contemplated to include nanoclays (also referred to as nanocomposites), including organoclays, including polyolefins of the present invention, preferably including stable functional groups, preferably sharing functional functional groups. Are combined.

  The organoclay is a phosphonium derivative of one or more ammonium, primary alkyl ammonium, secondary alkyl ammonium, tertiary alkyl ammonium, quaternary alkyl ammonium, aliphatic, aromatic or aryl aliphatic amine, phosphine or sulfide, Sulfonium derivatives of aliphatic, aromatic or aryl aliphatic amines, phosphines or sulfides can be included.

  Organoclay is montmorillonite, sodium montmorillonite, calcium montmorillonite, magnesium montmorillonite, nontronite, beidellite, vorcon score, laponite, hectorite, saponite, soconite, magadite, kenyaite, sobockite, svinordite, stevensite, vermiculite, halloysite, It can be selected from one or more of aluminate oxide, hydrotalcite, illite, rectolite, tarosovite, ladykite and / or fluorine mica.

  The organoclay is preferably present at 0.1 to 50% by weight, based on the total weight of the nanocomposite. The stable functional group can be selected from one or more of phenol, ketone, hindered amine, substituted phenol, substituted ketone, substituted hindered amine, and combinations thereof.

  The nanocomposite can further comprise at least one elastomeric ethylene-propylene copolymer. The at least one elastomeric ethylene-propylene copolymer can be present at 1-70% by weight, based on the total weight of the nanocomposite. Furthermore, the nanocomposite can further comprise at least one non-functional thermal polyolefin.

  Preferably, the stable functional groups are present in at least one stability functionalized thermoplastic, and the organoclays are each present in an effective amount in the nanocomposite, so that the molded sample of the nanocomposite by heat. The hindrance of aging is 10% when compared to a control nanocomposite made with a thermoplastic polyolefin containing functional groups substantially free of covalently stable functional groups. In one embodiment, the stable functional group can be present at 0.01 to 15% by weight based on the total weight of the at least one stable functionalized thermoplastic material in the at least one stable functionalized thermoplastic polyolefin.

  The non-functionalized thermoplastic polyolefin is preferably miscible with at least one first stable functionalized thermoplastic polyolefin. In such embodiments, the at least one unfunctionalized thermoplastic polyolefin can also be present in the nanocomposite at 1 to 40% by weight, based on the total weight of the nanocomposite, and the organoclay is nanocomposite. It can be present in the nanocomposite at 0.5-40% by weight, based on the total weight of the material. Preferably, both the at least one first stable functionalized thermoplastic polyolefin and the at least one unfunctionalized thermoplastic polyolefin each comprise either polypropylene or polyethylene.

In other embodiments, nanocomposites suitable for use in the adhesives of the present invention can include:
a) at least one first non-functionalized polypropylene present in the nanocomposite at 10 to 98% by weight, based on the total weight of the nanocomposite;
b) at least one second polypropylene comprising a stable functional group, wherein the stable functional group is selected from one or more of phenol, ketone, hindered amine, substituted phenol, substituted ketone, substituted hindered amine or combinations thereof. The stable functional group is present in the stable functionalized polypropylene at 0.05 to 15% by weight, based on the total weight of the polypropylene containing the stable functional group;
At least one second polypropylene comprising a stable functional group is present in the nanocomposite at 10 to 90% by weight, based on the total weight of the nanocomposite;
c) Organoclay. Here, the organoclay is hexyl ammonium ion, octyl ammonium ion, 2-ethylhexyl ammonium ion, dodecyl ammonium ion, octadecyl ammonium ion, dioctyl dimethyl ammonium ion, trioctyl ammonium ion, distearyl ammonium ion, ammonium salt, pyridinium salt, Including one or more of a sulfonium salt, a phosphonium salt, or a combination thereof. In addition, organoclay is further montmorillonite, sodium montmorillonite, calcium montmorillonite, magnesium montmorillonite, nontronite, beidellite, vorcon score, laponite, hectorite, saponite, sauconite, magadite, kenyaite, sobockite, svindordite, stevensite, vermiculite , Clays selected from one or more of: halloysite, aluminate oxide, hydrotalcite, illite, rectolite, tarosovite, ladykite or fluorine mica. Also, the organoclay is present in the nanocomposite at 1-30% by weight, based on the total weight of the nanocomposite; and d) optionally, 2-70% by weight, based on the total weight of the nanocomposite. And further comprising one or more of an ethylene-propylene elastomer copolymer or isobutylene rubber present in the nanocomposite.

In other embodiments, the additive can include one or more adhesion promoters such as polar acids, polyaminoamides (eg, Versamid 115, 125, 140 commercially available from Henkel), urethanes (eg, isocyanates). / Hydroxy-terminated polyester systems, for example, binder TN / Mondur Cb-75, commercially available from Miles, coupling agents (for example, silane ester (Z-6020), commercially available from Dow Corning), titanate (commercially available from Kenrich) Kr-44), reactive acrylic acid monomers (eg, Sarbox SB-600 available from Sartomer), metal acid salts (eg, Sarat 633 available from Sartomer), polyphenylene oxide, oxidized polyolefin, acid-modified polyolefin. Fin, and anhydride modified polyolefin.

Oil content Preferred oil content includes aliphatic naphthenic oil, white oil and the like. Particularly preferred oils include paraffinic or naphthenic oils such as Primol 352 or Primol 876 (commercially available from ExxonMobil Chemical France, SA, Paris, France).

Plasticizers Preferred plasticizers include mineral oil, polybutene, phthalate and the like. Preferred plasticizers include phthalates such as di-iso-undecyl phthalate (DIUP), di-iso-nonyl phthalate (DINP), dioctyl phthalate (DOP), combinations thereof, and / or derivatives thereof.

  Particularly preferred plasticizers include polybutenes, such as Parapol 950 and Parapol 1300, which were previously available from ExxonMobil Chemical Company (Houston, Texas).

  Preferred plasticizers are polyalphaolefins (PAO), high purity hydrocarbon liquid compositions (HPFC) and group III base stocks such as those described in WO 2004/014998, page 16, line 14 to page 24, line 1. Including. Particularly preferred PAOs include decene oligomers and decene and dodecene co-oligomers. A preferred PAO is commercially available from ExxonMobil Chemical Company (Houston, Texas) under the trade name Supersyn. In a preferred embodiment, the PAO, HPFC or Group III base stock is present at 0.5-60% by weight, based on the weight of the polymer and the PAO, HPFC or Group III base stock.

Wax Preferred waxes include polar or nonpolar waxes, polypropylene waxes, polyethylene waxes and wax modifiers. Particularly preferred waxes are polar wax, non-polar wax, Fischer-Tropsch wax, oxidized Fischer-Tropsch wax, hydroxy stearamide wax, functionalized wax, polypropylene wax, polyethylene wax, wax modifier, amorphous wax, carnauba wax , Castor oil wax, microcrystalline wax, beeswax, carnauba wax, castor wax, plant wax, candelilla wax, Japanese wax, ouricury wax, rice bran wax bark, rice bran wax, jojoba wax, bay wax, montan wax, ozo Kelite wax, earring, ceresin wax, petroleum wax, paraffin wax, polyethylene wax, chemically modified hydrocarbon wax , Substituted amide waxes, and can be selected from the group consisting of and derivatives. In some embodiments, polar and nonpolar waxes can be used simultaneously in the same composition.

Low molecular weight polymers and other additives include low molecular weight polymers (i.e. low Mn polymers, where low means Mn of 5000 or less, preferably 4000 or less, more preferably 3000 or less, more preferably 2500 or less. To do). Preferred low Mn polymers include low α-olefin polymers, such as propylene, butene, pentene, hexene, etc. (eg, polyα-olefins including propylene, butene, pentene, and / or hexene, number average) The molecular weight is 5000 g / mol or less). Particularly preferred polymers include polybutenes with Mn less than 1000. An example of such a polymer is commercially available from ExxonMobil Chemical Company under the trade name PARAPOL®. PARAPOL® 950 is a liquid polybutene polymer having a Mn of about 950 and a kinematic viscosity of 220 centistokes (cSt) at 100 ° C. as measured by ASTM D445.

Ester polymer In other embodiments, the additive may comprise one or more ester polymers (polyesters). In a preferred embodiment, the additive comprises a blend of two (or more) phase systems, where the polyester is a discontinuous phase and the phase comprising a-srPP-g-FG is a continuous phase.

Other additives Other preferred additives include blocking agents, antiblocking agents, pigments, dyes, colorants, processing aids, UV stabilizers, lubricants such as polydimethylsiloxane and calcium stearate, adjuvants, surfactants Agent, color masterbatch, fluidity improver, crystallization aid, plasticizer, oil component, stabilizer, antioxidant, polymer additive, antifoaming agent, preservative, thickener, flow modifier, moisturizing agent Agents, fillers, water and the like.

  Polymer additives can include homopoly-alpha-olefins, alpha-olefin copolymers, diolefin copolymers and terpolymers, elastomers, polyesters, block copolymers, ester polymers, acrylate polymers, alkyl acrylate polymers and vinyl acetate polymers. .

Adhesive Composition The adhesive composition (eg, polymer blend) of the present invention comprises a polyolefin rich in one or more amorphous syndiotactics and / or a polyolefin rich in one or more functional syndiotactics. Can do. In a preferred embodiment, the adhesive of the present invention comprises an amorphous syndiotactic rich polyolefin, an amorphous syndiotactic rich polyolefin functionalized with functional groups, or a combination thereof, wherein the amorphous syndiotactic Otectic-rich polyolefins include: about 5% by weight or more of C3-C40 α-olefins; about 50% to about 80% r dyads based on the total number of r and m dyads present in the polymer; The heat of fusion is 10 J / g or less according to the procedure described in ASTM E 794-85; and the ash content is 1% by weight or less, wherein the functional group, if present, has a weight average molecular weight of 1000 or less, and carbon- Including compounds containing carbon double bonds, carbon-carbon triple bonds, and / or heteroatoms; Including an adhesive having a peel strength for non-polar substrates of about 3.5 lb / inch or more and a peel strength for polar substrates of about 0.5 lb / inch, wherein the peel strength is ASTM D-1876 as described herein. Measure according to

  In addition, the adhesive composition of the present invention can include one or more of the above-described additives, and the weight ratio of polyolefin to additive is mixed at about 1: 1000 to 1000: 1. Preferably, the weight ratio is about 1: 100, about 1:50, about 1:20, about 1:10, about 1: 5, about 1: 4, about 1: 3, about 1: 2, or about 1: 1. It is. Alternatively, the weight ratio is about 100: 1, about 50: 1, about 20: 1, about 10: 1, about 5: 1, about 4: 1, about 3: 1, or about 2: 1.

  The adhesive compositions (eg, polymer blends) of the present invention can include one or more amorphous syndiotactic rich polyolefins and / or one or more functional syndiotactic rich polyolefins. In addition, the adhesive composition of the present invention can include one or more of the above-described additives and is mixed such that the polymer blend includes 10-90 wt% additive, based on the weight of the polymer blend. Preferably, the polymer blend is 20-80% by weight additive, more preferably 30-80% by weight additive, more preferably 40-80% by weight additive, even more preferably 50-80% by weight. Product, more preferably 60-80% by weight additive, even more preferably 70-80% by weight additive, based on the weight of the polymer blend.

  In the method used to produce the adhesive composition of the present invention, no particular restrictions are necessary regarding the mixing method. Therefore, the raw materials can be uniformly mixed using a Henschel mixer or the like, and then melted, mixed and formed into pellets using an extruder or the like. It is also possible to use a Brabender mixer, whereby mixing and melting are performed simultaneously, and after melting, the material can be directly formed into a film, sheet or the like. Thus, the blends described herein can be formed using conventional techniques known to those skilled in the art, and therefore the blend can be one or more static mixers, in-line mixers, elbows, orifices, baffles or This can be achieved using a combination of these.

  In a preferred embodiment, the adhesive composition comprises an amorphous syndiotactic rich polyolefin blend, more preferably amorphous syndiotactic, present at about 1 to about 99 weight percent based on the total weight of the blend. Is present in an amount of about 5% by weight or more based on the total weight of the adhesive composition, preferably about 10% or more, preferably about 20% or more, preferably about 30% or more, preferably It is present at about 40% or more, preferably about 50% or more, preferably about 60% or more, preferably about 70% or more, preferably about 80% or more, preferably about 90% or more.

  In a preferred embodiment, the adhesive composition comprises a blend containing a polyolefin rich in functional amorphous syndiotactic present at about 1 to about 99 weight percent based on the total weight of the blend, more preferably the amorphous. The syndiotactic rich polyolefin is present in about 5% by weight or more, preferably about 10% by weight or more, preferably about 20% by weight or more, preferably about 30% by weight or more, based on the total weight of the adhesive composition. Preferably about 40% by weight or more, preferably about 50% by weight or more, preferably about 60% by weight or more, preferably about 70% by weight or more, preferably about 80% by weight or more, preferably about 90% by weight or more. To do.

  In a preferred embodiment, the adhesive composition comprises a blend containing polypropylene that is rich in amorphous syndiotactic present at about 1 to about 99 weight percent based on the total weight of the blend, more preferably the amorphous syndiotactic. The tick-rich polyolefin is present in about 5% by weight or more based on the total weight of the adhesive composition, preferably about 10% by weight or more, preferably about 20% by weight or more, preferably about 30% by weight or more, preferably Is present at about 40% or more, preferably about 50% or more, preferably about 60% or more, preferably about 70% or more, preferably about 80% or more, preferably about 90% or more.

  In a preferred embodiment, the adhesive composition comprises a blend containing a polypropylene rich in amorphous syndiotactic functionalized with maleic anhydride, present at about 1 to about 99% by weight, based on the total weight of the blend. And more preferably the amorphous syndiotactic rich polyolefin is present in about 5 wt% or more, preferably about 10 wt% or more, preferably about 20 wt% or more, based on the total weight of the adhesive composition, Preferably about 30% by weight or more, preferably about 40% by weight or more, preferably about 50% by weight or more, preferably about 60% by weight or more, preferably about 70% by weight or more, preferably about 80% by weight or more, preferably Present at about 90% by weight or more.

  In one embodiment, the adhesive composition comprises less than 3 wt% antioxidant, less than 3 wt% low viscosity flow improver, less than 10 wt% wax, and / or less than 3 wt% crystallization aid. Contains agents. In some embodiments, however, the wax may be undesirable and is present in less than 5 wt%, preferably less than 3 wt%, more preferably less than 1 wt%, more preferably based on the weight of the adhesive composition. Is present at less than 0.5% by weight.

  In other embodiments, the adhesive composition of the present invention comprises amorphous syndiotactic rich polypropylene, and any combination of the adhesives described above is less than 50% total based on the weight of the adhesive composition , Preferably less than 25 wt%, preferably less than 20 wt%, preferably less than 15 wt%, preferably less than 10 wt%, preferably less than 5 wt%.

  In other embodiments, the adhesive composition of the present invention comprises a polypropylene rich in amorphous syndiotactic functionalized with maleic anhydride, and any combination of the aforementioned adhesives is based on the weight of the adhesive composition. The total amount is less than 50% by weight, preferably less than 25% by weight, preferably less than 20% by weight, preferably less than 15% by weight, preferably less than 10% by weight, preferably less than 5% by weight.

Adhesive Composition Properties The adhesive compositions of the present invention preferably have a peel strength of about 3.5 lb / in or greater as measured according to modified ASTM D-1876 against non-polar substrates (eg, isotactic polypropylene). is there. Preferably, the peel strength for a polar substrate (eg, Mylar) is about 0.5 lb / in or more, more preferably about 1.0 lb / in or more.

  As shown by the fiber tear example here, the adhesive composition of the present invention has excellent adhesive properties to cellulose and other similar materials. The adhesive composition of the present invention preferably has a set time of less than about 10 minutes, more preferably less than about 1 minute, and even more preferably less than about 30 seconds. Fixing time is defined as the time it takes to compress the bonded substrate construct to fix it together with sufficient adhesion for use herein, so that when torn, substrate fiber tearing is obtained, and thus the bond Is strong enough to remove compression. The bond is thought to strengthen with further cooling, but no further compression is required. These fixation times were measured by placing the adhesive melt dots on a file holder substrate taped to a flat desk. A file holder tag (1 inch × 3 inch (2.5 cm × 7.6 cm)) was placed on the dot after 3 seconds and compressed with a 500 g weight. The weight was left for about 0.5 to about 10 seconds. The construct so formed was peeled away to ensure a sufficient level of binding to cause substrate fiber tearing. The fixed time was recorded as the minimum time required for this binding to occur. A commercially available standard adhesive was used to calibrate this process.

  The adhesive composition of the present invention has a substrate fiber tear rate of 75% to 100% at 25 ° C. An adhesion test swatch was made by bonding together the substrate and a portion of the molten adhesive (eg, dots), and the bond was compressed until cooled to room temperature (ie, about 25 ° C.). The dot size was controlled by the adhesion volume, so in most cases the formed compression disc formed a uniform circle just inside the substrate area. Once the construct was generated, various damages were caused to evaluate the effect of binding. The low temperature fiber tear test placed a bond sample in a freezer or refrigerator to obtain the desired test temperature. Substrate fiber tear at room temperature aged the sample at ambient conditions. The bonds were separated by hand and measured for the type of damage observed. The amount of substrate fiber tear is expressed here as a percentage.

Use of Adhesive Compositions Each of the above desired adhesive compositions has a final property and suitability for a specific application, such as stereoregularity type (stereoregularity), melting point, average molecular weight, molecular weight distribution, monomer and comonomer type. And the level, sequence distribution, presence or absence of other functional groups, and the type and amount of adhesive additives utilized therein.

  The adhesive composition of the present invention can be used for any adhesive application, including but not limited to disposables, packaging, laminates, pressure sensitive adhesives, tapes, labels, wood bonds, paper bonds, nonwovens, road markings, reflective coatings. Etc. can be used.

Disposable Products In a preferred embodiment, the adhesive composition of the present invention can be used in disposable diaper and napkin fuselage structures, elastic joints for disposable product conversion, packaging, labels, bookbinding, woodworking, and other assembly applications. Particularly preferred uses include: baby diaper leg elastics, diaper face tape, diaper leg cuffs, diaper torso structure, diaper center stabilization, diaper liquid transfer layer, diaper outer cover layered structure, diaper rubber cuff layered structure, for women Napkin center stabilization, ladies napkin adhesive stripping, industrial filtering bonding, industrial filter material layered structure, filter mask layered structure, surgical clothing layered structure, surgical wear layered structure, and perishable product packaging.

  In one embodiment, the adhesive composition of the present invention can be applied to at least a portion of one or more disposable products such as nonwovens, nonwoven fibers, non-elastic nonwovens, elastic nonwovens, necked-bonded laminates, Stretch-bonded laminates, spunbond-meltblown laminates, polypropylene spunbond layers, polyethylene layers, polyethylene and polypropylene spunbond mixed layers, elastic strands, styrene-isoprene-styrene, styrene-butadiene-styrene, styrene-ethylene / Propylene-styrene, styrene-co-butadiene-styrene, polyurethane, woven fabric, polypropylene, polyester, body fluid impermeable back sheet, body fluid impermeable layer, body fluid permeable layer, body fluid permeable cover, absorption , Tissue, elastic material, super absorbent polymer, polyolefin film, polyester film, polyvinyl chloride film, polyvinylidene film, polyvinylidene chloride film, polyvinyl acetate film, elastic adhesive tape, front tape backing, wood, paper, barrier film, film Laminate, nonwoven composite material, fiber material, woven material, durable fiber, absorbent, elastic strand, elastic fiber, thin fabric, film, cover stock material, nonwoven polyethylene, perforated polyethylene, super absorbent polymer, filament, porous fiber Fiber, velcro tape material, spunbond nonwoven material, lining, elastic side plate, fixing tape, elastic band, rayon, nylon, cellulosic pulp, cellulosic cotton and super absorbent core.

  Further, a disposable material consistent with the present invention can include the adhesive composition of the present invention disclosed herein, wherein the adhesive is applied to at least a portion of one or more disposable items, such as diapers, Training pants, sanitary napkins, panty liners, incontinence clothing, bed pads, surgical gowns, surgical gowns, mousetraps, velcro, clothing, medical clothing, and swimwear. Similarly, the disposable item can include a second disposable item part bonded to the first disposable item part with the adhesive composition of the present invention.

  In one embodiment, the adhesive composition of the present invention comprises one or more solvents selected from the group consisting of hexane, heptane, mineral spirits, xylene, toluene, benzene, chlorinated hydrocarbons, and combinations or derivatives thereof. be able to.

  In one embodiment, the disposable article comprising the adhesive composition of the present invention can further comprise one or more antioxidants, such as tris (di-t-butyl-p-hydroxybenzyl) -trimethylbenzene, alkyl Bisphenol, zinc dibutyldithiocarbamate, 4,4′-methylenebis (2,6-di-tert-butylphenol), tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid) methane] , Ralyl stearyl thiodipropionate, dilauryl 3,3′-thiodipropionate, 2,6-di-tert-butyl-p-cresol, and combinations or derivatives thereof.

  Disposable articles comprising the adhesive composition of the present invention can further comprise one or more stabilizers, such as hindered phenol, sulfur phenol, phosphorus-containing phenol, 1,3,5-trimethyl-2,4,6. -Tris (3-5-di-tert-butyl-4-hydroxybenzyl) benzene, pentaerythritol tetrakis-3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, n-octadecyl-3 (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propionate, 4,4′-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-thiobis (6-tert-butyl-o-cresol) ), 2,6-di-tert-butylphenol, 6- (4-hydroxyphenoxy) -2,4-bis n-octylthio) -1,3,5-triazine, 2,4,6-tris (4-hydroxy-3,5-di-tert-butyl-phenoxy) -1,3,5-triazine, di-n- Octadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 2- (n-octylthio) ethyl-3,5-di-tert-butyl-4-hydroxybenzoate, sorbitol hexa- (3,3,3 5-di-tert-butyl-4-hydroxy-phenol) propionate, and combinations or derivatives thereof. In a preferred embodiment, the disposable article comprising the adhesive of the present invention is a consumer product.

In the laminate 1 embodiment, a laminate product comprising two or more layers may be in combination with the adhesive composition of the present invention. The laminate product can include two or more layers in combination with the adhesive composition of the present invention, wherein the adhesive composition is present between the layers. In one embodiment, a laminate product comprising two or more layers in combination with the adhesive composition of the present invention can comprise one or more materials, such as wood, plastic, paper, rubber, thermoplastic, cardboard. Metal, metal foil, metal-deposited surface, cloth, non-woven fabric, spunbond fiber, stone, gypsum, glass, rock, ceramics, film and foam.

  Further, a laminate product comprising two or more layers in combination with the adhesive composition of the present invention can comprise a laminate, wherein each layer is independently wood, plastic, paper, rubber, thermoplastic, cardboard. Selected from metal, metal foil, metal-deposited surface, cloth, non-woven fabric, spunbond fiber, stone, gypsum, glass, rock, ceramics, film and foam.

  A laminate product comprising two or more layers in combination with the adhesive composition of the present invention, wherein the two or more layers comprise a first layer and a second layer, the second layer comprising the first layer material and May be formed from different materials.

  In one embodiment, a laminate product comprising two or more layers in combination with the adhesive composition of the present invention can further comprise a release paper or release agent present on the surface layer. A laminate product comprising two or more layers in combination with the adhesive composition of the present invention can also include a laminate structure produced by any of spraying, extrusion, fusing, polymer injection, and hot melt bonding techniques. .

  In one embodiment, a laminate product comprising two or more layers in combination with an adhesive composition of the present invention further comprises at least one layer comprising a combination of the adhesive composition of the present invention and one or more of the following materials. The material can be, for example, wood, plastic, paper, rubber, thermoplastic, cardboard, metal, metal foil, metallized surface, cloth, non-woven fabric, spunbond fiber, stone, gypsum, glass, rock, ceramics, Films and foams.

  In a preferred embodiment, the laminate product can comprise two or more layers in combination with the adhesive composition of the present invention, wherein the adhesive composition has an open time of 60 seconds or less and an open time. Is measured according to ASTM D4497. In a preferred embodiment, the adhesive composition of the present invention, when used in a laminate product comprising two or more layers, has a fixing time of 3 seconds or more as measured by those skilled in the art.

  In a preferred embodiment, a laminate product comprising two or more layers in combination with the adhesive composition of the present invention has a substrate fiber tear rate of 75% to 100% at 22 ° C. as measured according to the method described herein. An adhesive can be included. In a preferred embodiment, the laminate product comprising two or more layers in combination with the adhesive composition of the present invention is a consumer product.

  Also, the adhesive composition described above can be applied to any substrate as a laminate, such as a polar substrate (eg, cardboard, mylar (polyester)), a non-polar substrate (eg, iPP), or both polar and non-polar substrates (For example, the middle). Preferred substrates are wood, paper, cardboard, plastic, thermoplastics, rubber, metal, metal foil (eg, aluminum foil and tin foil), metallized surfaces, cloth, non-woven (especially polypropylene spunbond fibers or non-wovens), span Bond fiber, cardboard, stone, gypsum, glass (including silicon oxide (SiOx) coating applied by depositing silicon oxide on the film surface), foam, rock, ceramics, film, polymer foam (eg, Polyurethane foam), ink-coated substrates, dyes, pigments, PVDC, etc., or combinations thereof. Another preferred substrate comprises the polymers described above as suitable for polyethylene, polypropylene, polyacrylate, acrylic, polyethylene terephthalate, or blends.

  Any of the aforementioned substrates and / or adhesive compositions of the present invention can be corona discharge treated, flame treated, electron beam irradiated, microwave, or silane treated before or after the substrate and adhesive composition are mixed.

  The adhesive compositions of the invention or their dosage forms can be applied directly to the substrate and / or can be sprayed or placed thereon. The composition may be melted or heated to a semi-solid state before or during application. Spraying is defined as including atomization, for example, formation of a uniform dot pattern, spiral spraying, such as Nordson-controlled fiberization or vibration of an elongated filament, using ITW Dynafiber / Omega head (Omega head). heads) or Summit technology from Nordson. The adhesive composition of the present invention may be melt blown. Melt blowing techniques include those described in US Pat. No. 5,145,689 and any method that uses an air stream to break up the filaments of the extrudate and then deposits the broken filaments on the substrate. Is defined as Typically, meltblowing technology is a method of rotating hot melt adhesive fibers with air and transporting them onto a bonding substrate. The fiber size can be easily controlled at 20-200 microns by changing the ratio of melt to air. Little or no free fibers are generated due to the inherent stability of the adhesive meltblowing device, preferably none at all. Under UV light, the bond appears as a regular, smooth, elongated dot pattern. Atomization can also be defined as a method of using air to atomize a hot melt adhesive, making it a very small dot and carrying it on a binding substrate.

Nonwoven / Fiber In certain embodiments, the adhesives of the invention can be used in textile products. The fiber product is made of a fibrous material and is coated with an adhesive composition. The fibrous material can include single component fibers, multiple component fibers, or combinations thereof. Several types of fibrous materials can be used to form a textile product, and are usually distinguished based on the fiber configuration within the textile product. For example, certain fibrous materials are assembled isotropically, and the individual fibers are arranged in a completely random state and do not have a preferred orientation in any of the three major spatial axes. Another example of a fibrous material is a textile yarn, which has a high degree of fiber orientation with respect to the main axis of the material. Textile yarns are produced from short (finite length) fibers by a combination of processing steps collectively referred to as spinning. After preliminary fiber placement, the fibers are twisted together and fixed together to form a spun yarn, where the spun yarn is continuous in length and substantially uniform. Yarns are usually used to form fabrics by weaving or knitting.

  Fibrous substances are cotton, kapok, coir, flax, hemp, ramie, jute, sisal, abaca, cellulose, wool, mohair, cashmere, human hair, goat hair, camel hair, llama hair, alpaca hair, bikuna Hair, silk, nylon, aramid, kevlar, nomax, polyamide, polyacrylate, polyolefin, polymers such as propylene, butene-1, polyethylene, polypropylene, and ethylene-vinyl acetate, polyesters such as polyethylene terephthalate, polybutylene terephthalate , Polyethylene terephthalate, and poly-ethyleneoxybenzoate, asbestos, polyamide, polycarbonate, polystyrene, thermoplastic elastomer, fluoropolymer, vinyl polymer, mineral, acrylic, polyvinyl chloride, Machine binder, glass, metal, alumina, silicon carbide, boron nitride, boron carbide, and combinations thereof.

  Typical textile products include nonwovens, carpets, carpet linings, diapers, swimwear, pediatric training pants, adult incontinence clothing, feminine care products, medical clothing, bed pads, surgical gowns, cloth linings, sponge scourers Automotive interior parts, clothing, tape, face masks and respirators, air filters, vacuum bags, oil and chemical adsorbents, heat insulating materials, first aid products, medical wrapping paper, fiber fillers, jackets, bed quilts These include stuffing, furniture stuffing, filter media, scrubbing wash, wiping material, and combinations thereof.

  In a preferred embodiment, the carpet comprises the adhesive composition of the present invention. In another preferred embodiment, the tape comprises the adhesive composition of the present invention.

  As used herein, “nonwoven fabric” refers to a fabric material produced by means other than weaving. In non-woven fabrics, the fibers are processed directly into a planar sheet-like fabric structure by going through an intermediate one-dimensional yarn, and then chemically or mechanically bonded (or both), cohesive fabric Is obtained. Nonwoven materials can include natural or synthetic fibers or mixtures thereof. Commonly used materials for forming nonwoven materials include rayon, polyester, polypropylene, polyethylene, nylon and others. The individual fibers are usually short fibers or continuous filaments. Typical fibers are polypropylene fiber, rayon fiber, polyester fiber, polyethylene fiber, nylon fiber, cellulose fiber, viscose fiber, ethylene-propylene copolymer fiber, polyolefin fiber, polyamide fiber, polycarbonate fiber, polystyrene fiber, thermoplastic elastomer fiber , Fluoropolymer fibers, vinyl polymer fibers, carbon fibers, glass fibers, mineral fibers, wool fibers, acrylic fibers, polyvinyl chloride fibers, polyurethane fibers, organic binder fibers and combinations thereof.

  In one embodiment, a textile product comprising a combination of one or more fibrous materials and the adhesive composition of the present invention can comprise a first backing material, wherein the fibrous material is a first backing material. And the adhesive is disposed on at least a portion of the fibrous material. The textile product can also include a combination of one or more fibrous materials and the adhesive composition of the present invention, including a first backing material and a second backing material adhered to the adhesive.

  The textile product can also include a combination of one or more fibrous materials and the adhesive composition of the present invention, wherein the first backing material is a jute fabric, slit polypropylene film fabric, burlap, needle punch material, Nonwoven polypropylene and combinations thereof.

  In one embodiment, a textile product comprising a combination of one or more fibrous materials and the adhesive composition of the present invention comprises a circle, an ellipse, a T-shape, a Y-shape, a cross shape, a hollow, a square, a polygon ( multifiber), laces, and / or fibrous materials having a polygonal cross-sectional shape.

  Accordingly, a textile product comprising a combination of one or more fibrous materials and the adhesive composition of the present invention comprises a garment, rug, insulation, carpet, composite material, printed circuit board, prepreg, wig, or combinations thereof. Can be included.

  Further, in one embodiment, where the textile product includes one or more fibrous materials in combination with the adhesive composition of the present invention, the adhesive composition can further include one or more additives, for example, an interface. Activators, foaming agents, polymer compatibilizers, flame retardants and water.

  In a preferred embodiment, the fiber product comprising a combination of one or more fibrous materials and the adhesive composition of the present invention has an adhesive composition as described above having a substrate fiber tear rate of 75% to 100% at 22 ° C. Any one of them. In a preferred embodiment, the textile product comprising a combination of one or more fibrous materials and the adhesive composition of the present invention is a consumer product.

In certain film embodiments, the polymer components described herein can be used in monolayer films. Alternatively, the polymer component can be applied to at least the outer portion of the monolayer film. A single layer film is sufficiently thick to assume a self-supporting form, while being flat enough to be able to move, bend or wrinkle without breaking. The film thickness depends on the application and product, but is usually 125 μm or less. Single layer films are non-oriented, uniaxially oriented, or biaxially oriented, and the polymer component is formed by application to at least a portion of the film substrate. Alternatively, the polymer component can be blended with a film substrate to change its properties.

  The film substrate can include paper, foil, metal, alloy, polyethylene, polypropylene, polyester, polyethylene terephthalate, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyamide, homopolymers thereof, and combinations and copolymers thereof.

  The monomer film may further comprise another polymer component selected from polyethylene, polypropylene, polyester, polyethylene terephthalate, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyamide, their homopolymers, combinations and copolymers thereof.

  In one embodiment, the film comprising the adhesive composition of the present invention preferably comprises a polypropylene layer and / or an oriented polypropyl layer, and / or a biaxially oriented polypropylene layer.

Hot Melt Adhesive In certain embodiments, the adhesive of the present invention can be used in a hot melt adhesive composition. Hot melt adhesives exist as solids at room temperature and can be converted to sticky liquids by the application of heat. Hot melt adhesives are usually applied to the substrate in molten form.

  In one embodiment, the hot melt adhesive composition comprising the adhesive composition of the present invention may comprise an adhesive composition having a substrate fiber tear rate of 75% to 100% at 25 ° C., preferably The substrate fiber tear rate at 25 ° C. is 95% to 100%. In one preferred embodiment, the hot melt adhesive composition comprising the adhesive composition of the present invention is a consumer product.

In a particular embodiment of the pressure sensitive adhesive 1, the adhesive composition described herein can be used in a pressure sensitive adhesive composition. As used herein, a “pressure sensitive adhesive composition” is an adhesive composition that has the ability to sufficiently wet the substrate and form useful bonds at room temperature or at about room temperature (about 25 ° C.) with moderate pressure. It is a thing. As used herein, the term “useful bond” varies depending on the substrate application and refers to a balance of adhesion and cohesive strength. In one embodiment, the pressure sensitive adhesive comprising the adhesive composition of the present invention has a fixing time of 30 minutes or less.

In certain embodiments of the tape, the adhesive of the present invention can be used on a tape. Tapes are usually configured to bond two or more substrates together. The tape includes an adhesive composition that is applied to a backing element. Backing part is polymer film, polyester film, polyolefin base film, polyurethane film, polyvinyl chloride foam (foams), polyethylene foam, nonwoven polyurethane, nonwoven polyester, woven fabric, face stock, paper, synthetic polymer material, plastic, polyolefin Polymers such as polyethylene and polypropylene, polyester, polyethylene terephthalate, polyvinyl chloride, kraft paper, polymer, laminate, latex-impregnated paper, foil, lithostock, lightweight stock, styrene foam, expanded polystyrene foam, It can be selected from the group comprising woven fabrics, non-woven fabrics, fabrics, crepe papers, thermoplastic elastomers, and combinations thereof. Typical backings have various thicknesses from 1 micron to several centimeters. Particularly preferred backings include oriented polypropylene, biaxially oriented polypropylene and polyvinyl chloride polymer. Oriented polypropylene, biaxially oriented polypropylene and polyvinyl chloride polymer films are particularly preferred backings.

  The tape is single-sided or double-sided, i.e., the adhesive material is applied to one or both sides of the backing material. The tape can include an adhesive composition and a release material attached to the opposite side of the backing. The double-sided tape can include a first adhesive composition and a second adhesive composition applied to the opposite side of the backing. At least one of the first adhesive composition or the second adhesive composition comprises an adhesive composition described herein, for example, either or both compositions comprise the adhesive composition of the present invention. .

  The tape can be configured so that various substrates, eg, the first substrate and the second substrate adhere to each other, or the tape can be configured to adhere a single substrate. The first substrate may be the same material as the second substrate, or these substrates may be formed of different materials. Either or both substrates are plastic, polyolefin, polymer, stainless steel, paper, paperboard, cardboard, cardboard, cardboard, plywood, kraft paper, cardboard, fiberboard, plastic resin, metal, alloy, foil, leather, Can include films, plastic films, laminates, clothing, containers, surgical instruments, medical devices, glass, and bedding.

  The tape can be provided in rolls, sheets, pads, or other shapes determined by the specific application, protecting the adhesive composition adhered to the backing to prevent unintentional adhesion to surfaces other than the intended substrate. To do. For example, the adhesive composition adhered to the backing can be attached to the release material until use. The release material is typically configured to be attached to and peelable from the tape to maintain the adhesive strength of the adhesive composition. The release material is typically used when the tape is supplied as a sheet or roll. The release material typically includes a release coating, such as silicon. Tape provided in roll form can be used with a tape dispenser or can be broken by hand. A tape provided in the form of a pad can include an adhesive composition between two release liners, at least one release liner being coated with a release coating composition.

  The adhesive composition can be applied to at least a portion of at least one side of the backing portion. Usually, the adhesive composition has the ability to sufficiently wet the substrate and form useful bonds at room temperature, or approximately at room temperature, under moderate pressure. As used herein, the term “useful bond” refers to the balance of adhesion (adhesion to substrate failure) and cohesive (internal adhesion failure) strength and is optimized according to the application of the tape. For example, an adhesive composition in a removable tape has a relatively low adhesive strength compared to the cohesive strength and can be peeled off without leaving a residue (eg, adhesive) on the substrate. Arise. In contrast, high performance tapes, such as those used in shipping and packaging, exhibit both high adhesion and high cohesive strength, resulting in substrate or backing failure.

In an embodiment of the packaging adhesive 1, the packaging adhesive can comprise the adhesive composition of the present invention. Packaging can also include the adhesive composition of the present invention, wherein the adhesive described herein is applied to at least a portion of one or more packaging members, such as paper, paperboard, cardboard, cardboard, cardboard. , Including plywood, craft, cardboard, fiberboard, plastic resin, metal, alloy, foil, film, plastic film, laminate, and bedding.

  In one embodiment, the present invention can include a package comprising the adhesive composition described herein, wherein the adhesive is one or more packages such as boxes, containers, frame boxes, cases, cardboard boxes, and trays. It is applied to at least a part of the member.

  The packaging can also include the adhesive composition of the present invention, where the adhesive is for cereal products, cracker products, beer packaging, frozen food products, paper bags, cups, milk packs, juice containers, goblets, and shipping products. It is applied to at least a part of one or more packaging members used for packaging the container.

Wood Processing In certain embodiments, the adhesives described herein can be used in wood processing. Wood processing includes the formation of a wood processed product by applying an adhesive composition to at least a portion of the structural member. The structural member can include a variety of materials, including but not limited to wood, plywood, or plastic or veneer. For example, the structural member can also include board, wood, fiberboard, gypsum board, gypsum, artificial wallboard, plywood, PVC, melamine, polyester, impregnated paper, and sheet lock. Wood processing can be used, for example, to form indoor furniture, outdoor furniture, decoration, molded articles, doors, window frames, windows, woodwork products, and luxury furniture. Accordingly, a preferred embodiment is a wood consumer product comprising the adhesive composition of the present invention.

Label In certain embodiments, the adhesive compositions described herein can be used in labels. Usually, the label is simply intended to adhere to the substrate. As such, the label is not intended to be a structural part. As a result, the label can have high internal strength and low adhesive strength.

  The label includes an adhesive composition coating layer on the backing and has a peelable surface on the opposite side of the adhesive composition. The release liner of the label is intended to be adhered to the label until the label is applied to the intended substrate. Label backings are well known in the art. Any suitable backing can be utilized in the present invention. Backing part is polymer film, polyester film, polyolefin-base film, polyurethane film, polyvinyl chloride film, polyvinyl chloride foam, polyethylene foam, nonwoven polyurethane, nonwoven polyester, knitted fabric, paper, synthetic polymer material, plastic, polyolefin, Polyethylene, polypropylene, polyester, polyethylene terephthalate, polyvinyl chloride, kraft paper, polymer, laminate, latex-impregnated paper, foil, lithostock, lightweight stock, styrene foam, laminate foam, expanded polystyrene foam, For example, woven fabrics, non-woven fabrics, fabrics, crepe papers, thermoplastics, and mixtures with polyethylene and polypropylene can be included.

  Suitable substrates are plastic, polyolefin, stainless steel, paper, paperboard, cardboard, cardboard, cardboard, plywood, kraft paper, cardboard, fiberboard, plastic resin, metal, alloy, foil, leather, film, plastic film, Laminates, garments, containers, surgical instruments, medical equipment, glass, and bedding can be included, for example.

  The label may be in the form of a roll, sheet or other form determined by the particular application and is thus protected from unintentional adhesion to other surfaces. As described above, the label can be laminated to a release liner to prevent unexpected adhesion to other surfaces. The release liner for the label is supplied with a release coating such as silicone so that the release liner can be easily peeled from the label. A release liner is a sheet coated with a release material for use in a label. The release liner reproducibly provides a moderate level of release to the intended adhesive, is desired to have no adverse effect on the adhesive, and is aging resistant so that the release level can be relatively predicted over time Should.

  The label can include a backing, an adhesive composition, and a release liner. The adhesive composition can be applied to the backing and the release liner can be applied to the adhesive composition. Alternatively, the adhesive composition can be applied to the release liner and then the backing can be applied to the adhesive composition. The release liner can then be removed from the adhesive composition prior to applying the label to the substrate.

Bookbinding In certain embodiments, the adhesives of the present invention can be used for bookbinding. For convenience, the term “bookbinding” is a book having a joint and is used to describe a method of producing a book in which the adhesive composition is applied to at least a portion of the joint. However, the embodiments described herein are not limited to adhesive compositions that are suitable only for bookbinding. As used herein, the term “book” shall include other products including pages bound with an adhesive composition, such as paperbacks, soft cover books, instruction manuals, magazines, catalogs, trade journals, dictionaries, etc. It is.

  In one embodiment, a bound product comprising the adhesive composition of the present invention can comprise a bond comprising paper or a large amount of paper. In one embodiment, the adhesive of the present invention has a substrate fiber tear rate of 75% to 100% at 22 ° C. Preferably, the bookbinding product comprising the adhesive composition of the present invention is a consumer product.

In certain embodiments of road surface indications, the adhesive compositions described herein can be used in road surface indication compositions. The road marking composition typically includes one or more fillers applied to the binding composition and one or more substrates. The one or more substrates are asphalt, concrete, metal, brick, paving stone, ceramic, polymer material, lightweight concrete block, soft sport surface, playground surface, runway, tartan substitutes, concrete, metal, asphalt, bitumen , Brick, paving stone, tile, steel plate, wood, ceramic, polymer material, glass, concrete block, porcelain, stone, wood panel, particle board, wood vehicle parts, lightweight concrete block, scrim , And combinations thereof.

  The road marking composition includes one or more fillers to increase weatherability, visibility, covering power, abrasion resistance, adhesion, and / or reflectivity of the road marking composition. In addition, certain fillers can be added to improve the overall flow characteristics of the thermoplastic road marking, prevent separation of the road marking, provide resistance to the substrate applied to the bonding composition, and / or Or the cost of the road surface indicating composition can be reduced. Fillers that can be used for this purpose are sand, pigment, glass beads, polymer-based beads, calcium carbonate, crushed marble, gravel, dolomite, talc, glass pearl, prism reflector, lens reflector, calcite spar , Silica sand, graphite, dust ash, cement dust, clay, feldspar, aragonite, fumed silica, alumina, magnesium oxide, zinc oxide, barium sulfate, aluminum silicate, calcium silicate, tianates, chalk, Reflective inorganic filler, bulking filler, beads, calcium sulfate, calcium metasilicate, quartz powder, calcined flint powder, mica, calcium silicate glass fiber, dye, granite, gypsum, slaked lime, alumina, diatomaceous earth, reflector , Modifier, lead white, lithopone, Lom yellow, cadmium yellow, resin beads, polymeric gels, polymers, ceramic materials, crushed glass, stone, corundum, aluminum hydroxide, silicon oxide, glass spheres, and zinc neodecanoate and the like. Examples of dyes include titanium dioxide, zinc oxide, magnesium oxide, lead chromate, and mixtures thereof. The type and content of the pigment are selected according to the specific purpose of the road surface display and can be easily confirmed by those skilled in the art. Furthermore, one or more fillers can be added to the road surface indicating composition, and the road surface indicating composition can be given color, opacity, or hue.

  An important property of road marking compositions is that they are visible under all environmental conditions. Accordingly, the road surface display composition can include one or more reflective fillers. A road marking composition incorporating one or more reflective fillers maximizes the visibility of road markings in rain and darkness by reflecting the light of the car. One or more reflective fillers can be included in the road surface display composition in an amount sufficient to provide enhanced visibility of the composition by reflected light. Suitable reflective fillers include, but are not limited to glass beads, polymer beads, sand, silica compounds, ceramic materials, and / or other reflective fillers commonly used for such purposes in road marking compositions. Beads are preferred reflective fillers, including but not limited to polymer beads or glass beads. Glass beads are most preferred. The beads should not adversely affect the cohesive strength of the cooled binder, and therefore a strong bond must occur between the binder and the beads. The main requirement is that the beads are stable to the heat applied during road marking preparation, mixing and use. Preferably, the beads should remain stable when subjected to heat of at least 200 ° C. for about 20 minutes.

  Beads prepared from the polymer should be able to resist the pressure provided by normal traffic without being damaged or crushed. Furthermore, the reflective filler should be evenly distributed throughout the binder to provide uniformity in the road surface display characteristics and to provide long-life reflective characteristics. The uniform distribution of reflective filler results in new reflective filler exposure on the surface when the upper surface of the road marking is removed due to traffic wear and weathering. In addition, an increase in the amount of the reflective filler added to the road surface display composition helps maintain sufficient reflection characteristics over a long period of time while increasing the reflectivity of the road surface display. When the amount of reflective filler present in the road marking composition is small, the reflective ability deteriorates when the reflective filler dispersed in the composition is reduced due to tire wear, while in addition If the amount of the reflective filler is too large, the strength of the road surface display composition decreases.

  In a preferred embodiment, a road marking composition comprising an adhesive composition of the present invention and a binder comprising one or more fillers comprises a binder further comprising a copolymer having a Mw of 100,000 to 250,000.

  In one embodiment, a road marking composition comprising a binder comprising the adhesive composition of the present invention can also include one or more waxes, such as polar wax, nonpolar wax, Fischer-Tropsch wax, Oxidized Fischer-Tropsch wax, hydroxy stearamide wax, functionalized wax, polypropylene wax, polyethylene wax, wax modifier, maleic anhydride graft, polyethylene containing pendant acid functional groups, paraffin wax, microcrystalline wax, and these It is a combination.

  In one embodiment, a road marking composition comprising a binder comprising the adhesive composition of the present invention can also include one or more road marking additives such as plasticizers, oils, stabilizers, oxidations. Inhibitor, pigment, dye, polymer additive, defoamer, preservative, thickener, fluidity improver, moisturizer, extender, hindered phenol, phosphate, anti-sticking agent, lubricant, light stabilization Agents, ultraviolet absorbers, dispersants, thickeners, bases, wetting agents, flame retardants, crosslinking agents, curing agents, opacifiers, and water. Other such additives include oils and include aliphatic oils, naphthenic oils, white oils, soybean oils, combinations thereof, and derivatives thereof.

  The road marking composition comprising the binder comprising the adhesive composition of the present invention can further comprise one or more plasticizers, such as mineral oil, polybutene, phthalate, hydrocarbon oil, soybean oil, phthalate ester. , Elastomers, olefin oligomers, vegetable oils, cyclohexanedimethanol dibenzoate, and combinations thereof, and / or sand, pigments, glass beads, polymer-based beads, calcium carbonate, crushed marble, gravel, dolomite, talc, glass pearls, prisms Reflector, lens reflector, calcite spa, silica sand, graphite, dust ash, cement dust, clay, feldspar, aragonite, fumed silica, alumina, magnesium oxide, zinc oxide, barium sulfate, aluminum silicate, silica Calcium acid, cyanate titanates), chalk, reflective inorganic filler, bulking filler, beads, calcium sulfate, calcium metasilicate, quartz powder, calcined flint powder, calcium silicate glass fiber, dye, granite, gypsum, slaked lime, alumina, diatomaceous earth , Reflector, modifier, lead white, lithopone, chrome yellow, cadmium yellow, resin beads, polymer gel, polymer, ceramic material, crushed glass, stone, corundum, aluminum hydroxide, silicon oxide, glass bulb, and neodecanoic acid Zinc is mentioned.

  In a preferred embodiment, a road marking composition comprising an adhesive composition of the present invention and a binder comprising one or more fillers comprises a binder comprising one or more modifiers, for example Succinic anhydride modified polymers and metal oxides.

  When used in a road marking composition, the filler is effective in increasing the strength of the road marking and maintaining the thickness of the road marking. However, the use of excessive amounts of fillers can result in a fragile road surface indication. As a result, the road marking composition contains 20 to 90% by weight of one or more fillers. In one aspect, the one or more fillers comprise 50% by weight or less, or 10-40% by weight, or 15-30% by weight of one or more beads. In yet another aspect, the one or more fillers comprise 20 weight percent or less, or 2 to 15 weight percent, or 3 to 10 weight percent of one or more dyes.

  In one aspect, the road marking composition comprises 10-80% by weight of a binder and the binder composition comprises a polymer of the invention described herein.

  Preferably, the road marking composition comprising a binder comprising the adhesive composition of the present invention comprises 30% by weight or less of one or more waxes and / or 80% by weight or less of one or more tackifiers, and / or Or 20% by weight or less of one or more plasticizers, and / or 5% by weight or less of one or more acid-modified tackifiers or polymers, and / or 5% by weight or less of one or more stabilizers, and / or 40 A binder comprising no more than 1% by weight of one or more polymer additives and / or no more than 10% by weight of one or more opacifier and / or no more than 1% by weight of one or more antioxidants. In a preferred embodiment, the road surface display composition containing the binder containing the adhesive composition of the present invention has a luminance of 70 or more.

Sealant In a particular embodiment, the adhesive composition described herein can be used in a sealant composition. The purpose of the sealant is to maintain a seal between the two surfaces of one substrate, thus repairing the substrate or otherwise achieving and maintaining a seal between the two sets of substrates. Accordingly, a sealant composition comprising a mixture comprising the adhesive composition of the present invention is applied to at least a portion of the substrate surface to which the mixture is sealed.

  Substrates include concrete, roofing, marble, anodized aluminum, brick, mortar, granite, limestone, porcelain, glass, painted surface, wood, polyvinyl chloride, polyacrylate, polycarbonate, polyethylene, cloth, filling, plastic, Stone, masonry material, pipe, hose, metal, wiring, ski, polyethylene, polypropylene, polyester, acrylic, PVDC, paper, ethylene, vinyl acetate, automobile, building, airplane, panel, deck, bone, pavement, automobile, etc. Can include tailboards, door panels, wheelhouses, rocker panels, fire walls, floor ring edges, trunks, and floor pans. For example, the sealant composition can be used to repair leaking pipes or cracked windshields of automobiles. The sealant further provides a load bearing elastic bond between two or more surfaces, preventing the passage of air, water and dust.

  The sealant composition is not only useful for filling gaps and bonding substrate surfaces during repair operations, but can also be used to bond the first substrate to other substrates. The automotive industry in particular uses sealants primarily for this purpose. Automobiles are assembled from several structural parts and joined together in various ways depending on the particular parts and the degree of stress that must be withstood by the parts. For example, the sealing material is used for assembling door panels, quarter panels, tail plates of automobiles, and roofing materials. Other automotive assemblies that are welded or bolted together use a sealant composition at the seam. Further examples of automotive applications using sealants are wheelhouses, impact reducers, rocker panels, fire walls, floor ring edges, floor pans, and trunks.

  Regardless of the purpose of use, the sealant composition is a gap filling material. Thus, at the time of sealing formation, the sealing composition should have a sufficiently low elasticity so that it can flow into and fill the gaps in the substrate to which the sealing composition is applied, and the sealing material After the material has hardened and cured, it should still be sufficiently filled so that the substrate is sealed. In the uncured state, the sealing composition should remain tacky and have a viscosity low enough to ensure proper substrate wetness.

  The sealant composition is preferably essentially non-sticky to contact once solidified or cured. In the cured state, the sealant should have sufficient durability to withstand the normal climate and user exposure in various applications. First, the sealant should provide an effective barrier against oxygen, water, and air. The cured sealant should be resistant to cracking and shrinkage against mechanical stresses such as substrate expansion at high temperatures, so the sealant does not sag or flow over time. In particular, glass substrates can crack at high levels of stress. The sealant must be stiff enough to retain its normal shape and dimensions, but it must also maintain sufficient flexibility to exhibit a substantial recovery against elongation. Therefore, a balance between high bond strength and high elongation and low tensile modulus is desirable for mixtures used as sealants. High bond strength compositions typically provide an effective seal the higher the bond strength and the greater the force required to remove the substrate from the mixture. The elongation of the mixture refers to the ability of the composition to return to its approximate original configuration after being subjected to a specified tensile elongation. High elongation is desirable to provide a sealant with very high self-healing properties. That is, the sealant deforms to accommodate the stress exerted on the sealed portion of the substrate.

  In a preferred embodiment, the sealant mixture further comprises one or more waxes, for example polar wax, nonpolar wax, Fischer-Tropsch wax, oxidized Fischer-Tropsch wax, hydroxy stearamide wax, functionalized wax, polypropylene wax. , Polyethylene wax, wax modifier, amorphous wax, carnauba wax, castor oil wax, microcrystalline wax, beeswax, carnauba wax, castor wax, whale wax, plant wax, candelilla wax, Japanese wax, our waxy wax, Douglas Farbark wax, rice bran wax, jojoba wax, bayberry wax, montan wax, peat wax, ozokerite wax, ceresin wax A petroleum wax, paraffin wax, polyethylene wax, chemically modified hydrocarbon wax, substituted amide wax, and combinations and derivatives thereof.

  In one embodiment, a sealant composition comprising a mixture comprising the adhesive composition of the present invention may further comprise one or more additives, including a plasticizer, an oil component, a stabilizer, an antioxidant, Dye, anti-sticking agent, processing aid, neutralizing agent, water, dye, polymer additive, antifoaming agent, preservative, thickener, fluidity improver, moisturizer, extender, water, crosslinking agent, thixotrope Agent, surfactant, adhesion promoter, reinforcing agent, chain extender, UV stabilizer, colorant, organic solvent, stabilizer, desiccant, wetting agent, nucleating agent, accelerator, curing agent, and these Combinations or derivatives are mentioned.

  In one embodiment, a sealant composition comprising a mixture comprising the adhesive composition of the present invention can further comprise one or more fillers, such as silica, diatomaceous earth, calcium carbonate, iron oxide, hydrogenated. Castor oil, fumed silica, precipitated calcium carbonate, hydrophobic treated fumed silica, hydrophobic precipitated calcium carbonate, talc, zinc oxide, polyvinyl chloride powder, fungicide, graphite, carbon black, asphalt, carbon filler, clay, Mica, fiber, titanium dioxide, cadmium sulfide, asbestos, wood powder, polyethylene powder, chopped fiber, foam, beads, thixotrope, bentonite, calcium sulfate, calcium oxide, magnesium oxide, and combinations or derivatives thereof.

  In one embodiment, a sealant composition comprising a mixture comprising the adhesive composition of the present invention can further comprise one or more adhesion promoters, such as silane, titanate, organosilane, acrylic Acid, anhydride, epoxy resin, curing agent, polyamide, methyl acrylate, epoxy, phenol resin, polyisobutylene, aminoalkyl, mercaptoalkyl, epoxyalkyl, ureidoalkyl, carboxy, acrylate and isocyanurate functionalized silane, mercaptopropyltri Methoxysilane, glycidoxypropyltrimethoxysilane, aminopropyltriethoxysilane, aminoethylaminopropyltrimethoxysilane, ureidopropyltrimethyloxysilane, bis-γ-trimethoxysilyl-propylurea, 1,3 5-tris-γ-trimethoxysilylpropyl isocyanurate, bis-γ-trimethoxysilylpropylmaleic acid, fumaric acid and γ-methacryloxypropyltrimethoxysilane, aminopropyltriethoxysilane, and combinations and derivatives thereof .

  In one embodiment, a sealant composition comprising a mixture comprising the adhesive composition of the present invention can further comprise one or more crosslinking agents, such as oxime crosslinking agents, alkoxysilanes, epoxyalkylalkoxysilanes. Amide silane, aminosilane, enoxysilane, tetraethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, glycidoxypropyltrimethoxysilane, vinyl tris-isopropenoxysilane, methyl tris-isopropenoxysilane, methyl tris-cyclohexylaminosilane , Methyl tris-secondary butylaminosilane, polyisocyanate, and combinations or derivatives thereof.

  In one embodiment, a sealant composition comprising a mixture comprising the adhesive composition of the present invention can further comprise one or more organic solvents, such as aliphatic solvents, alicyclic solvents, mineral spirits. , Aromatic solvents, hexane, cyclohexane, benzene, toluene, xylene, and combinations or derivatives thereof.

  In one embodiment, a sealant composition comprising a mixture comprising the adhesive composition of the present invention can further comprise one or more surfactants, such as a vinyl-containing or mercapto-containing polyorganosiloxane, vinyl Macromonomers containing terminal polydimethylsiloxane, combinations or derivatives thereof.

  In one embodiment, a sealant composition comprising a mixture comprising the adhesive composition of the present invention can further comprise one or more chain extenders, such as aminosilane, amidosilane, acetoxysilane, and aminoxy Silane, methylvinylbis-N, -methylacetamidosilane, methylhydrogendiacetoxysilane, dimethylbis-diethylhydroxyaminosilane, dimethylbis-secondary butylminosilane, polyisocyanate, and combinations or derivatives thereof.

  In one embodiment, a sealant composition comprising a mixture comprising the adhesive composition of the present invention can further comprise one or more antioxidants, such as thioesters, phosphates, hindered phenols, Tetrakis (methylene 3- (3 ′, 5′-di-t-butyl-4hydroxyphenyl) propionate) methane, 2,2′-ethylidenebis (4,6-di-tert-butylphenol), 1,1 -3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6, tris- (3,5-tert-butyl-4-hydroxy Benzyl) benzene, dilauryl thiodipropionate, pentaerythritol tetrakis (β-lauryl thiopropionate), alkyl-aryl-di- and polyline Salt, thiophosphorous acid salts, and combinations or derivatives thereof.

  In one embodiment, a sealant composition comprising a mixture comprising the adhesive composition of the present invention may comprise up to 30% by weight of one or more waxes.

Paving Compositions In certain embodiments, the adhesive compositions described herein can be used in paving compositions. Typically, paving compositions include asphalt, gravel and adhesive compositions. As used herein, the term “asphalt” refers to various substances that are solid or semi-solid at room temperature, usually liquefied upon heating, the main constituent being natural bitumen (bitumen) obtained as a residue in petroleum refining It is. Asphalt is further defined by Kirk-Othmer, Encyclopedia of Chemical Technology, Volume 3, 3rd Edition, (1978), pages 284-327, John Wiley & Sons, New York. . Further explanation is given in the literature title “A Brief Introduction to Asphalt and some of its Use”, manual series no. 5 (MS-5), The Asphalt Institute, 7th edition, 1974, September.

  Examples of natural bitumen include natural asphalt or petroleum refined asphalt, asphaltite, pyrogenic distillate, bottom stock, and other pyrogenic residues such as pyrogenic asphalt, petroleum pitch, coal tar pitch, and these A mixture is mentioned. Such materials are often characterized by a pass rate (ASTM D-5-51) of 0-300 or higher, preferably about 40-300, with a softening point in the range of about 32-120 ° C. Yes, preferably 38-65 ° C.

  Useful sources of asphalt include many of those currently on the market. For example, natural asphalt and petroleum asphalt are known to be used for roofing and paving applications. Natural asphalts include, for example, asphaltite such as gilsonite, grahamite and grans pitch; lake asphalt such as Trinidad asphalt; and rock asphalt. Petroleum asphalt is straight asphalt obtained by distillation of crude oil (non-blown and substantially non-oxidized), blown asphalt produced by blowing oxygen-containing gas into straight asphalt in the presence or absence of catalyst, propane or other The solvent extracted asphalt obtained when the asphalt material is separated from the petroleum fraction, and cutback asphalt, which is a mixture of straight asphalt and light oil solvent. The asphalt can also include petroleum tar and asphalt cement. Petroleum tar is obtained from petroleum fraction, refined tar, cutback tar obtained by mixing light oil fraction and tar, and tar pitch which is a residue obtained by removing volatile fraction from the tar. Contains petroleum gas tar that is obtained as a by-product when gas is produced. Any of these types of asphalt can be used alone or in combination. For example, straight asphalt is useful for paving applications, and oxidized and blown asphalt is useful for roofing applications.

  The paving composition of the present invention is particularly useful for the preparation of asphalt coating compositions. These include gravel-containing asphalt and are used, for example, for pavement of roads, bridges, airport runways and sidewalks and their partial repair or splicing. The paving composition of the present invention can be mixed with gravel in the fluid or molten state. Generally, the pavement composition is mixed with previously heated and dried gravel to form a uniform mixture of uniform gravel coats. The gravel can be heated under conditions of sufficient time and temperature to remove essentially all moisture prior to mixing. During mixing, the paving composition is typically at a temperature of about 100 ° C to about 160 ° C. Prior to cooling the final composition to a temperature that loses its processability, it can be spread on the roadbed, for example, then compressed and cured. After curing, the resulting pavement composition contains cohesive bonds with asphalt binder.

  The term “aggregation” as used herein is intended to include solid particles ranging in size from fine particles such as sand to relatively coarse particles such as crushed stone, gravel or slag. In general, such gravel used in the preparation of paving compositions is mainly inorganic materials, i.e., for example, crushed rocks, stones and possibly sand. The size of the gravel will depend somewhat on the desired end use of the particular paving composition. For example, larger gravel is typically used to lay on a new or re-paved roadway compared to a crush repair composition that typically includes gravel with a small average particle size. Of course, gravel can be highly irregular, especially when ground or ground. Examples of gravel materials include inorganic materials such as sand, gravel, crushed stone, and certain organic materials, such as recycled tire materials and thermoplastic materials, and mixtures of one or more inorganic and organic materials. is there. Other inorganic and organic materials known to be useful as gravel can also be used in the compositions of the present invention, although not explicitly shown here.

  The paving composition of the present invention is also useful for the preparation of improved seal coats. The seal coat is usually applied as warm asphalt, cutback asphalt, or asphalt emulsion. Molten or fluid asphalt is usually sprayed from a truck and gravel is placed on top of the asphalt, followed by rolling or compressing the gravel into the asphalt and finishing the application.

  The pavement composition of the present invention can be processed by conventional techniques after formation, for example to maintain it in a flowing or molten state under road construction conditions. For example, asphalt can be formed into cutbacks by flowing a suitable volatile solvent or distillate and asphalt. The cutback asphalt can then be mixed directly with gravel and in a fluid form as a paving composition, sometimes at room temperature. Another conventional technique for fluidizing asphalt prior to mixing with gravel to form a paving composition is to emulsify the asphalt by known techniques. The advantage of this fluidization method is that it can be applied as a paving composition at room temperature after mixing with gravel.

  An important technical consideration in pavement composition production is to ensure chemical compatibility of both the asphalt cement and the intended end use of the pavement composition. With regard to chemical compatibility, factors such as the presence of undesirable salts in the gravel must be taken into account to minimize the disintegration potential of the asphalt pavement composition.

  Furthermore, it is also necessary that the gravel and asphalt cement contained in the pavement composition have good tackiness, so that the asphalt composition is completely “wet” both before and after the asphalt pavement composition is laid on the surface. Ensure sufficient mixing of these materials. In addition, the physical characteristics of the gravel must be taken into account, i.e. a mixture that is suitable for the expected mode of use under specific conditions where high traffic and / or heavy loads are expected. it can.

  As such, the paving composition comprises an adhesive comprising the inventive polymer described herein. Preferably, the paving composition containing asphalt, gravel and the adhesive composition of the present invention is one or more natural asphalt, petroleum asphalt, or any combination thereof, and / or asphaltite, gilsonite, grahamite, glance pitch. , Lakea asphalt, Trinidad asphalt, or rock asphalt, and / or clay, stone, sand, rock, gravel, and slag, and / or carbon black, mine chatt, mine tailings, hard brick, husk, ash , Ground tire, clay, and glass.

  In a preferred embodiment, the paving composition containing asphalt, gravel and the adhesive composition of the present invention comprises 95% or less gravel.

  In another embodiment, the paving composition containing asphalt, gravel and the adhesive composition of the present invention comprises 90-96% by weight gravel.

  In another embodiment, the paving composition containing asphalt, gravel and the adhesive composition of the present invention comprises 80-99% by weight asphalt.

Stick glue In certain embodiments, the adhesive compositions described herein can be used in a stick glue. Stick glues are sold in various forms, one of which is a hot melt adhesive glue gun. Hot melt adhesive stick glues are usually designed for use with glue guns. The glue gun is adapted using a melting chamber to be grasped in the user's hand, and the distal portion of the stick glue receives the heat supplied to the melting chamber and is melted. The melting of the hot melt adhesive stick glue can be accomplished by pressing the hot melt adhesive stick glue into the melt chamber. When the hot melt adhesive stick paste is filled into the melting chamber and melted there, molten adhesive is provided from the gun nozzle. Accordingly, the hot melt adhesive stick paste is heated to a use temperature sufficient to provide a molten paste to the substrate. Substrates are paper, paperboard, cardboard, cardboard, cardboard, plywood, craft, cardboard, fiberboard, plastic resin, metal, alloy, foil, film, plastic film, laminate, sheet, wood, plastic, polystyrene, nylon, Polycarbonate, polypropylene, expanded styrene, porous substrate, polyvinyl chloride, walls, polyester, or combinations thereof can be included.

  The hot melt adhesive stick glue operating temperature is adjusted to produce a sufficiently low adhesive melt viscosity to ensure sufficient wetting of the substrate and provide sufficient opening time to fix the position of the substrate after paste application . Desirably, the adhesive composition becomes substantially non-tacky after cooling to about room temperature or below. The adhesive used in the hot melt adhesive stick glue should also have the ability to bond to various substrates.

  The other stick glue is a pressure sensitive adhesive stick glue. Pressure sensitive adhesive stick glue is a commercial product that includes a solid adhesive body contained within a container. Normally, the container is closed with a removable lid, which has an open part at the bottom. The open portion is a plane perpendicular to the axis of the pressure sensitive adhesive stick. The lid can be removed when it is desired to use a pressure sensitive adhesive stick glue.

  The pressure sensitive adhesive stick glue does not require heating when used on the substrate, and the adhesive is applied onto the substrate simply by applying pressure. Similarly, glue applied from a stick glue is sticky at room temperature, so that the substrate can then be adhered and attached to another substrate simply by applying pressure.

  In a pressure sensitive adhesive, at least one adhesive composition component is liquid at room temperature. The liquid component provides pressure sensitive or surface tack to the pressure sensitive adhesive stick paste at room temperature. Polymer additives, tackifiers, and / or plasticizers are often added to the adhesive composition so that the stick glue is tacky and a portion thereof remains on the substrate upon contact.

  Stick glue can be composed of a mixture of adhesive polymer, tackifier and wax. The amount of ingredients will vary depending on the application so as to give the adhesive composition an appropriate blend of melting point, operating temperature, open time, bond strength, durability and heat resistance. Adhesive compositions that accept stress well without compromising adhesion are desirable and are measured by bond strength and time to bond failure. Both the bond strength and the time to bond failure of the stick glue composition are preferably high. The longer the time to bond failure, the greater the flexibility of the paste.

  In a preferred embodiment, a stick glue comprising an elongated member comprises the adhesive composition of the present invention, wherein the adhesive further comprises a plasticizer, an oil, a stabilizer, an antioxidant, a synergist. , Pigments, dyes, polymer additives, antifoaming agents, preservatives, thickeners, fluidity improvers, moisturizers, fillers, water, fragrances, flame retardants, colorants, antibiotics, disinfectants, antifungal agents One or more additives such as inorganic salts, gelling agents, binders, surfactants, bases, antibacterial agents, and anti-foaming agents, and / or one or more such as one or more polyethylene, titanium oxide, and calcium carbonate Containing fillers.

  In one preferred embodiment, a stick glue comprising an elongated composition comprising the adhesive composition of the present invention comprises 5-30% by weight of one or more inorganic salts.

  In a preferred embodiment, a stick glue comprising an elongated composition comprising the adhesive composition of the present invention comprises up to 5% by weight of one or more colorants, dyes, antioxidants, perfumes, or pigments.

  In a preferred embodiment, a stick glue comprising an elongated composition comprising the adhesive composition of the present invention comprises 1% by weight or less of one or more antimicrobial agents.

  In a preferred embodiment, a stick glue comprising an elongated configuration comprising the adhesive composition of the present invention has a substrate fiber tear rate of 75% to 100% at 25 ° C.

In certain embodiments of pipe coating , the adhesive of the present invention can be used in pipe coating materials. Pipe coating materials or pipe wraps can be used to insulate or repair leaks in pressure vessels, industrial ships, transformers, pipes, fittings, tanks, containers and containers. In addition, pipe coating materials can be used on various types of surfaces, such as flat wall surfaces, circular joints and other mechanical parts. The pipe coating materials described herein can be used in various industries, such as architecture, building, construction, food, beverage, mining, petrochemical, oil, gas, and water treatment.

  Pipe coating materials are typically formed by applying an adhesive composition to at least a portion of a coating member. The covering member is glass fiber, fiber, woven fabric, non-woven fabric, fabric, cloth, polyethylene, polypropylene, acrylic rubber, EPDM, nitrile rubber, nylon, epichlorohydrin elastomer, polysulfide, acrylic elastomer, or butyl rubber, polyisobutylene. Can be included, for example. Pipe coating materials are wood, cement, concrete, non-woven fabric, woven fabric, aluminum, stainless steel, brass, nickel, glass, glazed ceramic, unglazed ceramic, tile, polyvinyl chloride, polyethylene terephthalate, gypsum, stucco, asphalt coating, roof For example, it can be formed from a blow felt, a synthetic polymer film, and a foamed polyurethane insulation. The covering member has an arbitrary thickness. For example, the thickness of the covering member used in a general private building is 1.27 mm.

  Accordingly, the pipe coating material comprising the adhesive composition of the present invention and the covering member can include an adhesive disposed on or in at least a part of the covering member.

  In a preferred embodiment, the pipe coating material comprising the adhesive composition of the present invention comprises one or more polymer adhesives, such as butyl rubber and polyisobutylene. More preferably, the pipe coating material comprising the adhesive composition of the present invention is a consumer product.

Safety Glass In certain embodiments, the adhesives described herein can be used in safety glass. There are two types of safety glass, laminated safety glass and tempered safety glass. Laminated safety glass typically reduces high frequency sound conduction and blocks 97% of ultraviolet light. Tempered safety glass is an integral glass strengthened by rapidly heating and cooling the glass to harden it, thereby increasing the glass strength.

  As used herein, “safety glass” is a material including transparent window glass. An important function of safety glass is that the adhesive composition used therein is not affected by temperature changes and the adhesive composition holds the glass piece in case the glass breaks. It is. Furthermore, the adhesive composition absorbs the shear stress applied to the safety glass due to the different expansion rates of the glass components, for example the safety glass comprises glass as the first layer and polycarbonate as the second layer. Is the case. Safety glass typically includes a plurality of material layers and an adhesive layer that is applied between the outside of one layer or between two or more layers to adhere to each other. The transparent window glass is formed by applying an adhesive composition to one or more transparent panels, and the adhesive composition can form a film on the one or more transparent panels. The one or more transparent panels can be formed from polyvinyl butyral, polyurethane, vinyl acetate, polyethylene, polypropylene, polycarbonate, glass, silicate glass, or combinations thereof.

  In one embodiment, the material comprising the transparent glazing comprises one or more transparent panels and comprises the adhesive composition of the present invention applied to at least a portion of the one or more panels. More preferably, the material comprises one or more transparent panels and a transparent glazing comprising the adhesive composition of the present invention, wherein the adhesive composition is applied to at least a portion of the one or more panels, wherein 1 The above transparent panel includes polyvinyl butyral, polyurethane, vinyl acetate, polyethylene, polypropylene, polycarbonate, glass, silicate glass, or a combination thereof. In a preferred embodiment, the material is bulletproof glass, soundproof glass, and / or safety glass. Furthermore, the adhesive composition of the present invention can form a film on one or more of the transparent panels.

Single roofing sheet In certain embodiments, the adhesive of the present invention can be used on a single roofing sheet. Single roofing sheets are usually formed from a roofing member and an adhesive that bonds the roofing member to the roof. The roofing member is typically formed from sheet metal, such as copper, turn-plated stainless steel, zinc, aluminum or alloys thereof.

  Important criteria for roofing boards include: resistance to compression when the roofing boards are packed in piles for transport, a relatively low melting temperature that allows automatic sealing without the use of heating equipment, and between bonded surfaces Includes strong bonds, high wind resistance, and excellent low temperature stability. Another important consideration is the ability to retain adhesive properties after exposure to sunlight for more than 2 hours, including excellent resistance to photooxidation.

  Furthermore, the adhesive composition should exhibit “move” characteristics at low temperatures of 32 ° C. to 37 ° C. in order to provide stronger adhesion and excellent wind resistance. As used herein, “move” refers to the case where the adhesive composition partially flows into the contact surface of the roofing material.

  Accordingly, in one embodiment, the roofing sheet includes a roofing member having a first side and a second side, wherein the adhesive composition of the present invention is applied to at least a portion of the second side. . In other embodiments, the roofing member comprises sheet metal, copper, steel, zinc, aluminum, combinations thereof and alloys thereof, roofing asphalt, fabric, gravel, and combinations thereof. Further, both sides of the roofing member can include rubber, glass fiber, aramid, carbon, polyester, nylon, asphalt, and / or sheet metal, where the sheet metal is copper, aluminum, combinations thereof, or Including these alloys.

  In a preferred embodiment, a roofing member having a first side and a second side has an adhesive composition of the present invention applied to at least a portion of the second side, the adhesive further comprising one or more A bitumen material is included, preferably the one or more bitumen materials include asphalt, and more preferably, the adhesive composition includes 80 wt% or less of one or more bitumen materials.

Reflective Coating In certain embodiments, the adhesive composition of the present invention can be used in reflective products. A reflective product is formed by applying a reflective material to a substrate surface, and provides a reflective power to a portion of the substrate. The amount of reflector can include materials known to those skilled in the art. For example, the reflective material can include prisms and glass beads. Substrate surfaces are roads, bicycle lanes, road markings, soft competition surfaces, playground surfaces, ships, runways, pedestrian crossings, buildings, tennis courts, roadways, artificial turf substitutes, oilfield drilling equipment, concrete, metal, asphalt, bitumen Brick, paving stone, tile, steel plate, wood, ceramic, polymer material, glass, abutment, road obstacle, barrier, pipe, pillar, guardrail, concrete block, sidewalk curb, parking lot, porcelain, stone, wood panel, Includes slabs, wood auto parts, lightweight concrete blocks, glass windows, traffic drums, traffic cones, liquid crystal displays, lighting, copiers, electronic backboards, diffuse white standards, and photographic light sources it can.

The adhesive composition is applied to at least a part of the reflective material to adhere the reflective material to the substrate. The adhesive composition includes the inventive polymer described herein.
Reflective products include roads, bicycle lanes, road markings, soft competition surfaces, playground surfaces, ships, runways, pedestrian crossings, buildings, tennis courts, roadways, artificial turf substitutes, oil field drilling equipment, concrete, metal, asphalt, Bitumen, brick, paving stone, tile, steel plate, wood, ceramic, polymer material, glass, abutment, road obstacle, barrier, pipe, pillar, guardrail, concrete block, sidewalk curb, parking lot, porcelain, stone, wood panel , Chipboard, wood auto parts, lightweight concrete block, glass window, traffic drum, traffic cone, liquid crystal display, lighting, copy machine, electronic backboard, diffuse white standard, and photographic light source More selected substrate surfaces can be included.

  In a preferred embodiment, the reflective article comprises a reflective material with the adhesive composition of the present invention applied to at least a portion of the substrate surface, the reflective material having a brightness of 70 or greater.

Other Products In one embodiment, the polymer of the present invention may be an injection molded product, a film, an extruded film, a cast film, or a combination thereof. The product preferably comprises an amorphous syndiotactic rich polypropylene and / or an amorphous syndiotactic rich polypropylene functionalized with maleic anhydride. The product can also include a polyolefin rich in amorphous syndiotactic disposed on a non-polar substrate, a polar substrate, or both. Therefore, the product of the present invention is on wood, paper, cardboard, plastic, thermoplastic, rubber, metal, metal foil, metalized surface, cloth, non-woven fiber, spunbond fiber, stone, gypsum, glass, film substrate SiOx coating applied by depositing silicon oxide, foam, rock, ceramic, film, polymer foam, ink coated substrate, dye coated substrate, dye coated substrate, PVDC, polyethylene, polypropylene, polyacrylic acid, acrylic acid, Polyolefins rich in amorphous syndiotactic and / or disposed on polyethylene terephthalate, corona release treated substrate, flame treated substrate, electron beam emitting substrate, gamma emitting substrate, electron wave treating substrate, silanized substrate and combinations thereof and / or Or a polyolefin rich in functional amorphous syndiotactic It can contain emissions.

The masterbatch also includes a masterbatch process that provides the polymer of the present invention to produce a variety of polymeric materials such as products, films, etc., and the polyolefin of the present invention and at least one additive under high shear conditions May be melt blended to produce a concentrate comprising 10-90% by weight of the polymer of the invention, and then the other components of the final product may be blended. Examples of suitable adhesives include the adhesives described herein. Amorphous syndiotactic rich polyolefin of the present invention, preferably amorphous syndiotactic rich polypropylene, functionalized amorphous syndiotactic rich polyolefin, preferably maleic anhydride grafted amorphous syndiotactic Rich polyolefin can be used in the masterbatch as both diluent and concentrate material and subsequently added to the final product. In one embodiment, the process of producing a masterbatch can include a step in which an amorphous syndiotactic rich polyolefin is functionalized simultaneously with the formation of a concentrate.

Example
Preparation of a-srPP Samples a-srPP-1-, a-srPP-3-, a-srPP-4-, a-srPP-5- and a-srPPr-6 polymerization liquid filled, one step 0.5 In a continuous stainless steel autoclave reactor, diphenylmethylene (fluorenyl) (cyclopentadienyl) hafnium dimethyl previously activated with N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was used. The reactor includes a stirring device, a water cooling / steam heating unit having a temperature control device, and a pressure control device. The solvent and propylene were purified by passing through a three column purification system before being sent into the reactor. All catalyst solutions were kept in an inert atmosphere with a water content of less than 1.5 ppm and sent into the reactor by a metering pump. Contact between the catalyst and the monomer occurred in the reactor.

  The reactor was first cleaned by continuously pumping hexane and scavenger through the reactor system at the maximum possible temperature (about 150 ° C.) for at least 1 hour. After washing, the reactor was heated / cooled to the desired temperature using a water / steam mixture flowing through the reactor jacket and controlled at the set pressure with a controlled solvent flow. Monomer and catalyst solutions were sent into the reactor when operation reached steady state. An automatic temperature control system was used to control and maintain the reactor at the set temperature. The onset of polymerization activity was inferred by observing the release of viscous product and the temperature drop of the water mixture. When the activity settled and the system reached equilibrium, the reactor was removed from the line while operating the system under the achieved conditions for at least 5 times the average residence time before collecting the sample. The final mixture containing mainly solvent, polymer and unreacted monomer was collected in a collection box after the system operation reached steady state. Methanol was used as a catalyst deactivator. The collected sample was first air dried in a hood to evaporate most of the solvent, and then dried in a vacuum oven at a temperature of about 90 ° C. for about 12 hours. The sample dried in the vacuum oven was weighed to obtain a yield. All reactions were conducted at a pressure of about 350 psig and a temperature range of 80-120 ° C. Detailed experimental conditions and polymer properties are listed in the table below.

  In this example, the polymerization temperature was varied to change the molecular weight and stereoregularity of the polymer. The resulting polymer has a% [r] dyad of about 58-75%. Moreover, each essentially shows an amorphous polymer.

A polypropylene sample rich in a-srPP functionalized amorphous syndiotactic was then functionalized by dissolving about 120 g of polymer in toluene, resulting in a polymer solution having a polymer concentration of about 20 wt%. 15 wt% maleic anhydride (based on the specific a-srPP used) is then added to the solution and 2.5 wt% radical initiator 2,5-dimethyl-2,5-di (t-butyl). Peroxy) hexane was added together. The reaction temperature is 139 ° C. for about 4 hours. An amide functional group was obtained by using 1-vinyl-2-pyrrolidone, and an acid functional group was obtained by using acrylic acid.

The data is shown below.

Characterization and Testing For purposes of the present invention and claims, the following tests are used unless otherwise indicated.

  Tensile strength (tensile break strength and elongation at break) is measured according to ASTM D 1708. Elongation at break is also referred to herein as tensile break elongation or elongation.

  Peel strength (also referred to as peel adhesive strength at an angle of 180 °, 180 ° peel strength, 180 ° peel strength, T-peel strength, also referred to as T-peel) is measured according to a modified version of ASTM D-1876 (0. 5 inch wide sample and 2 ″ per minute separation speed (modified to use 2 ″ per minute separation speed).

  Tensile strength modulus and Young's modulus at 100% elongation are measured according to ASTM E-1708.

  The dynamic storage modulus (also referred to as storage modulus) is G ′ and is measured as follows. In general, samples are tested using a three-point bend structure (TA Instruments DMA 2980). A solid rectangular compression-molded rod is placed on two fixed fulcrums and is periodically deformed by a movable fastener at the midpoint of the sample at a frequency of 1 Hz and an amplitude of 20 μm. The sample is first cooled to -130 ° C and then heated to 60 ° C at a heating rate of 3 ° C / min. In some cases, compression molded bars can be tested using other deformation settings: double cantilever bending and tensile elongation (Rheometrics RSAII). Under these settings, periodic deformation is applied at a frequency of 1 Hz and a strain amplitude of 0.05%. The sample is cooled to -130 ° C and then heated to 60 ° C at a rate of 2 ° C / min.

  Creep resistance is measured using ASTM D-2293, and creep is also referred to as sagging.

  Rolling ball tack is measured using PSTC6.

  Hot shear strength is measured by hanging a 1000 g weight from a 25 mm wide strip of Mylar (polyester) film coated with a polymer or adhesive bonded to a stainless steel plate with a contact area of 12.5 mm × 25 mm. The sample is placed in a 40 ° C. ventilation oven. Record the time until stress failure occurs.

  Probe tack (also called polyken probe tack) is measured according to ASTM D2979.

  Holding power is measured according to PSTC 7, also called shear holding power or shear strength.

  Density is measured at 25 ° C. according to ASTM D792.

  Gardner color is measured according to ASTM D-1544-68.

  Luminance is the reflectivity “Y” in CIE color coordinates determined by ASTM D 1925 divided by 100.

  The needle penetration test is measured according to ASTM D5.

  The bond strength is measured according to ASTM D3983.

  The adhesion to the road surface is measured according to ASTM D4541.

  Fixing time is defined herein as the time required to fix a compression bonded substrate construct that is capable of tearing substrate fibers when teared together with sufficient adhesion. These fixation times were measured by placing adhesive melt dots on a file holder substrate that was taped to a flat table. A file holder tag (1 inch × 3 inch (2.5 cm × 7.6 cm)) was placed on the dot after 3 seconds and compressed with a 500 g weight. The weight was left for about 0.5 to about 10 seconds. The construct so formed was peeled away to ensure a sufficient level of binding to cause substrate fiber tearing. The fixed time was recorded as the minimum time required for this binding to occur. The standard used a commercial adhesive to calibrate this process.

Molecular weights (number average molecular weight (Mn), weight average molecular weight (Mw), and z average molecular weight (Mz)) are measured by differential refractive index detector (DRI), online low angle light scattering (LALLS) detector, and viscometer (VIS). ) With Waters 150 size exclusion chromatography (SEC). Details of detector calibration are described elsewhere [Literature: T.W. Sun, P.M. Brant, R.A. R. Chance, and W.C. W. Graessley, Macromolecules, vol. 34, no. 19, 6812-6820 (2001)]; SEC using three Polymer Laboratories PL gel 10 mm mix-B columns, nominal flow rate of 0.5 cm ³ / min, and nominal injection volume of 300 microliters for both detector configurations. Common to Various transfer lines, columns and differential refractometers (DRI detector, used primarily for eluent concentration determination) were included in an oven maintained at 135 ° C.

  The LALLS detector is a model 2040 double angle light scattering photometer (Precision Detector Inc.). The flow cell placed in a SEC oven uses a 690 nm diode laser source and collects scattered light at two angles, 15 ° and 90 °. Only 15 ° emission was used in these experiments. The signal is sent to a data acquisition board (National Instruments), which accumulates measurements at a rate of 16 / sec. The four lowest measurements are averaged, and then the proportional signal is SEC- Sent to a LALLS-VIS computer A LALLS detector was placed behind the SEC column and before the viscometer.

  The viscometer is a high temperature model 150R (Viscotek Corporation). It consists of four capillaries and two pressure transducers arranged in a Wheatstone bridge configuration. One transducer measures the total pressure drop across the detector and the other transducer is placed across the bridge to measure the differential pressure. The specific viscosity of the solution flowing through the viscometer was calculated from these measurements. The viscometer was in the SEC oven and was placed behind the LALLS detector and before the DRI detector.

  The solvent for the SEC experiment is to add 6 g of butylated hydroxytoluene (BHT) as an antioxidant to a 4 liter bottle of 1,2,4 trichlorobenzene (TCB) (Aldrich reagent grade) and wait for dissolution of BHT. Prepared. The TCB mixture was then filtered through a 0.7 micron glass pre-filter followed by a 0.1 micron Teflon filter. In addition, there was another on-line 0.7 micron glass pre-filter / 0.22 micron Teflon filter assembly between the high pressure pump and the SEC column. The TCB was then degassed using an online degasser (Phenomenex, model DG-4000) before entering the SEC.

  The polymer solution was prepared by placing the dry polymer in a glass container and adding the desired amount of TCB, and then the mixture was heated at 160 ° C. with continuous agitation for about 2 hours. All amounts were measured gravimetrically. 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 ranged from 1.0 to 2.0 mg / ml, and low concentrations were used for high molecular weight samples.

  Prior to processing each sample, the DRI detector and injector were cleaned. The flow rate in the apparatus was then increased to 0.5 ml / min and the DRI was allowed to stabilize for 8-9 hours before injecting the first sample. The argon ion laser was fired for 1-1.5 hours, then the sample was run by firing the laser in standby mode for 20-30 minutes, and then the light control mode was switched to full power.

The g ′ index was measured using SEC with an on-line viscometer (SEC-VIS) and g ′ was recorded in the SEC trace for each molecular weight. The g ′ index is defined as g ′ = η _b / η _l : where η _b is the intrinsic viscosity of the branched polymer, and η _l is a linear chain having the same viscosity average molecular weight (Mv) as the branched polymer. It is the intrinsic viscosity of the polymer. η _l = KMvα, where K and α are linear polymer measurements and should be obtained with the same SEC-DRI-LS-VIS instrument used for g ′ index measurements. For polypropylene samples present in the present invention, K = 0.0002288 and α = 0.705 were used. Since the SEC-DRI-LS-VIS method measures intrinsic viscosity and molecular weight in individual elution volumes, it probably contains a narrowly dispersed polymer and does not require modification with respect to polydispersity. The linear polymer selected as a standard for comparison should have the same viscosity average molecular weight, monomer content, and composition distribution. The linear properties of polymers containing C2-C10 monomers are confirmed by carbon-13 NMR, Randall method (Rev. Macromol. Chem. Phys., C29 (2 & 3), pages 285-297). The linear properties of C11 and higher monomers are confirmed by GPC analysis using a MALLS detector. For example, for a propylene copolymer, the NMR should not show greater branching than the comonomer (ie, if the comonomer is butene, there should be no branching greater than 2 carbons). For propylene homopolymers, GPC should not show branching greater than one carbon atom. If a linear standard is desired for polymers where the comonomer is C9 or higher, T.W. Sun, P.M. Brant, R.A. R. Chance, and W.C. W. Graessley, Macromolecules, vol. 34, no. 19, 6812-6820 (2001). Reference can be made to the procedure for determining these polymer standards. In the case of syndiotactic polymers, the standard should have a syndiotacticity comparable to the amount measured by carbon-13 NMR. The viscosity average g ′ was calculated using the following formula:

  The maleic anhydride (MA) content of the maleated polymer was determined as follows. About 0.5 g of polymer was dissolved in 150 ml of toluene at the boiling point. Bromothymol blue was used as a color change indicator, and potentiometric titration containing TBAOH (tetra-butylammonium hydroxide) was performed on the heated solution. During the titration, the polymer did not precipitate.

  The Mooney viscosity measured ML1 + 4 at 125 ° C. according to ASTM D1646-90.

  Peak melting point (Tm), peak crystallization temperature (Tc), heat of fusion and crystallinity were measured according to ASTM E794-85 using the following procedure. Differential scanning calorimetry (DSC) data was obtained using a TA Instruments model 2920 instrument. A sample weighing about 7-10 mg was sealed in an aluminum sample pan. The DSC data was recorded by first cooling the sample to −50 ° C. and then gradually heating to 200 ° C. at a rate of 10 ° C./min. The sample was maintained at 200 ° C. for 5 minutes before beginning the second cooling-heating cycle. Both the first and second thermal cycle events were recorded. The area below the curve was measured and used to determine heat of fusion and crystallinity. The crystallization rate is calculated using the formula [area under the curve (joule / g) / B (joule / g)] × 100, where B is the heat of fusion of the main monomer component homopolymer. These B values are obtained from the Polymer Handbook, 4th edition, John Wiley and Sons, New York, 1999. The value 189 J / g (B) was used as the heat of fusion for 100% crystalline polypropylene. For polymers showing multiple melting points or crystallization peaks, the highest melting peak was taken as the melting point and the highest crystallization peak was taken as the peak crystallization temperature.

  Glass transition temperature (Tg) was measured according to ASTM E1356 using a TA Instruments model 2920 instrument.

  Melt Viscosity (ASTM D-3236) (also referred to as “viscosity”, “Brookfield Viscosity”) melt viscosity profile is usually measured using a Brookfield Thermosel viscometer and a No. Measurement was performed at a temperature of 120 ° C. to 190 ° C. using a 27 axis.

Adhesive test functionality a-srPPr or iPPr was thoroughly mixed and then degassed in a vacuum oven at 180 ° C and then cooled to 25 ° C. This was done before molding and bonding in order to eliminate the possibility of air bubbles in the next adhesive layer manufacture. Each functional a-srPPr sample was then molded into a thin sheet material approximately 0.4 mm thick at 180 ° C. for 10 seconds. To prepare a T-peel sample, this thin sheet adhesive sample was laminated between two Mylar substrates (0.003 ″ = 0.076 mm thick; used as received) at positive pressure and a temperature of 180 Teflon-coated at 10 ° C. and pressure 0.67 Mpa for 10 seconds A 3 mil cast film of metallocene homopolypropylene with a melt flow rate of 9 or less and a melting point of 150-151 ° C. for an iPP substrate has a lower bonding temperature of 150 ° C. All these adhesive / substrate laminates were cut into ½ "= 1.3 cm swatches. The adhesive thickness was ˜0.2-0.3 mm. T-peel measurements using three samples were performed according to a modified version of ASTM-1876, where the separation rate was 2 "/ min instead of 10" / min specified at room temperature on the Instron testing machine. Since samples available at min = 850 μm / s are limited, 0.5 ”wide samples were used. Adhesion was measured by average peel strength: peel strength = F / w, where F is peel strength. Yes, w is the width of the test sample AIF and CF are apparent interfacial failure (indicating adhesive remaining only on one mylar substrate) and cohesive failure (remaining on both mylar substrates) Each T-peel measurement uses 3 samples, so AIF / CF is 2 samples A It breaks in IF mode, which means that one sample breaks in CF mode, while CF / AIF means that two samples break in CF mode and one sample breaks in AIF mode. The following data shows a number of functional polyolefins.

  All functional srPPr polymers have higher adhesion to both Mylar and iPP compared to MA-iPPr. Thus, a-srPPr-g-MA improves adhesion to Mylar without sacrificing adhesion to iPP.

In the table below, some compositions are blends of a-srPPr or functional a-srPPr and a propylene-based polymer (POA), with or without tackifiers and / or waxes. POA homopolypropylene (denoted as aPP-iPP in the table) was prepared according to the general procedure described in USSN 10 / 868,951 filed on October 15, 2003. The catalysts used were di (p-triethylsilylphenyl) methylene (cyclopentadienyl) (3,8-di-t-butylfluorenyl) hafnium dimethyl (catalyst # 1) and rac-dimethylsilylbis (2- Methyl-4-phenylindenyl) zirconium dimethyl (catalyst # 2), and the activator used is N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate. Detailed polymerization conditions and polymer properties are listed in the table below.

E-5380 is ESCOREZ® 5380, a hydrogenated dicyclopentadiene based hydrocarbon resin having a ring and ball softening point of about 85 ° C., commercially available from ExxonMobil Chemical Company, Houston, TX. Yes.

E-2203 is ESCOREZ® 2203, which is an aliphatic-aromatic base hydrocarbon resin having a ring and ball softening point of about 93 ° C. E-5690 is ESCOREZ® 5690, which is a hydrogenated dicyclopentadiene-aromatic base hydrocarbon resin having a ring and ball softening point of about 89 ° C. Both are commercially available from ExxonMobil Chemical Company, Houston, TX. In the absence of functional polyolefin, both the composition PP-1 olefin PP-2 exhibits low adhesion to Mylar.

  As the data in the table above show, functional a-srPPr gives these compositions the advantage of T-peel strength to Mylar. Obviously, the functional group improves the adhesion of the propylene-based polymer to Mylar, as the MA group shows better results. Also, the viscosity (or molecular weight) of the propylene-based polymer can affect adhesion, since the intermediate molecular weight polymer, aPP-iPP-2, shows better results.

  Also, as the examples show, the compositions of the present invention provide enhanced adhesion to both polar and non-polar substrates. These can be applied to various areas, such as adhesives, tie layers, paint undercoats, adhesion promoters, interfacial agents, compatibilizing agents and the like. As noted above, some of the compositions of the present invention consist of component 1, aPP-iPP polymer and functional polyolefin such as a-srPPr-g-MA and other components such as tackifiers, waxes, antioxidants, plastic oils. The liquid resin tackifier and the like were prepared by blending at a high temperature under low or high shear mixing to form a molten fluid. Mixing temperatures vary from about 130 ° C to about 190 ° C.

Aliphatic-solvent based functionalized amorphous or low crystalline propylene based homopolymers and copolymers of a-srPP were prepared and functionalized in cyclohexane, hexane or a mixture of aliphatic solvents. After functionalization, the product can be left in solution, for example, optionally as a primer for TPO bumper coating adhesives, or for melt blending or film and molded tie layers, skin layers, adhesive compositions It can be dried for extrusion in other applications such as components in it. Important points regarding the inventive step include functionalization in aliphatic solvents, a) thus avoiding the use of aromatic solvents and environmental and process problems associated with aromatic solvents, and the base polymer is all the same solvent Opens up the possibility of being transported for production, functionalization and use, and b) the polymer solution can be used directly from the polymerization reactor for functionalization-inhibition final processing and redissolution steps.

Functionalization examples :
Comparative Example F1:
Polypropylene rich in 5.1 g of amorphous syndiotactic was dissolved in 500 ml of xylene at 130 ° C. 1.2 ml Luperox P (TERT-butyl peroxybenzoate, AtoFina Inc., Ontario, Canada) and 4 ml 1-vinyl-2-pyrrolidone were added to the solution. The solution was stirred for 2.5 hours. The product was precipitated in acetone and then further washed with acetone. The product was dried in vacuo at 120 ° C. overnight.

Comparative Example F2
Polypropylene rich in 50 g of amorphous syndiotactic was melted at 190 ° C. in a blender mixer. 2.0 g dicumyl peroxide and 4 ml vinyl-2-pyrrolidone were added and the mixture was stirred for 2.5 hours. The product was precipitated in acetone and the product was further washed with acetone. The product was dried in vacuo at 120 ° C. overnight.

Example F3
100 g of amorphous syndiotactic rich polyolefin was dissolved in 700 ml cyclohexane at 130 ° C. 3 g dicumyl peroxide, 10 g maleic anhydride was added to the solution. The solution was allowed to stir for 2.5 hours. The product was precipitated in acetone and the product was then further washed with acetone. The product was dried in vacuo at 120 ° C. overnight.

Example F4
100 g of amorphous syndiotactic rich polypropylene was dissolved in 700 ml of cyclohexane at 130 ° C. 3 g dicumyl peroxide and 4 ml 1-vinyl-2-pyrrolidone were added to the solution. The solution was allowed to stir for 2.5 hours. The product was precipitated in acetone and the product was then further washed with acetone. The product was dried in vacuo at 120 ° C. overnight.

Example F5
100 g of amorphous syndiotactic rich polypropylene was dissolved in 700 ml of cyclohexane at 130 ° C. 3 g dicumyl peroxide and 8 ml 1-vinyl-2-pyrrolidone were added to the solution. The solution was allowed to stir for 2.5 hours. The product was precipitated in acetone and the product was then further washed with acetone. The product was dried in vacuo at 120 ° C. overnight.

The results are shown below.

While the invention has been described with reference to illustrative embodiments, it will be apparent to those skilled in the art that various modifications can be made and equivalent components can be substituted without departing from the scope of the invention. Understood. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Accordingly, the invention is not limited to the specific embodiments disclosed as the best mode for carrying out the invention, but the invention is intended to include all embodiments included within the scope of the claims of the invention.

Claims (108)

A polyolefin amorphous syndiotactic rich containing C ₃ -C ₄₀ alpha-olefin of at least about 50 wt%:
Having from about 50% to about 80% r dyad based on the total number of r and m dyads present in the polymer; heat of fusion of 10 J / g or less; and ash content of 1% by weight or less. polymer. 2. The polymer of claim 1, having at least about 55% r dyad. The polymer of claim 1 having at least about 6.25% rpentad to about 31.6% rpentad based on the total number of r and m-pentad present in the polymer. 2. The polymer of claim 1 comprising greater than about 60% by weight propylene. The polymer of claim 1 further comprising at least 0.5 wt% ethylene, based on the total weight of the polymer. The polymer of claim 1, wherein the heat of fusion is not detectable. The polymer of claim 1 having an ash content of 0.1 wt% or less. The polymer of claim 1, wherein the density is from about 0.85 to about 0.88 g / ml. The polymer of claim 1 having a melt flow rate of 0.2 g / 10 min or more. The polymer of claim 1, wherein at least about 95% by weight of the polymer is soluble in hexane, cyclohexane, xylene or toluene at 25 ° C, based on the total weight of the polymer present. The polymer of claim 1 having a weight average molecular weight of about 5000 to about 5,000,000 g / mol. The polymer of claim 1 having a number average molecular weight of from about 5000 to about 3,000,000 g / mol. The polymer of claim 1, wherein the z-average molecular weight is from about 10,000 to about 10,000,000 g / mol. The polymer of claim 1, wherein the g 'index is from about 1.2 to about 1.5 as measured by the Mw of the polymer. 2. The polymer of claim 1 having no discernable crystallization temperature (Tc). Polymer blend containing:
Includes _C 3 _{-C 40} alpha-olefin of at least about 50 wt%, based on the total number of r and m dyads r dyads to about 50% to about 80% present in the polymer, a heat of fusion of 10J / g or less, And amorphous syndiotactic rich polyolefins with an ash content of 1% by weight or less; and C2-C40 polymers, C2-C40 copolymers, elastomers, random copolymers, impact copolymers, fractional polymers, tackifiers, crosslinks Agent, antioxidant, neutralizing agent, nucleating agent, filler, adhesion promoter, oil, plasticizer, wax, ester polymer, rubber reinforcing composition, recycled polymer, blocking agent, blocking agent, pigment, dye, Processing aids, UV stabilizers, lubricants, adjuvants, surfactants, color masterbatches, improved fluidity At least one additive comprising an agent, a crystallization aid, a polyalphaolefin, a Group III base stock, or a combination thereof. Additives are homopolypropylene, propylene copolymerized with up to 50% by weight of ethylene or C4 to C20 α-olefin, isotactic polypropylene, random copolymer of propylene and ethylene, random copolymer of polypropylene and butene or hexene, polybutene , ethylene vinyl acetate, a density 0.915~0.935g / cm ³ or less of polyethylene, linear polyethylene, density 0.86~0.90g / cm ³ or less of polyethylene, density 0.90~0.915g / cm ³ The following polyethylene, polyethylene having a density of 0.935 to 0.945 g / cm ³ or less, polyethylene having a density of 0.945 to 0.98 g / cm ³ or less, ethylene methyl acrylate, copolymer of acrylic acid, polymethyl methacrylic acid, polyvinyl chloride , Polybutene-1, isotactic polybutene, ABS resin, ethylene-propylene rubber, sulfurized EPR, EPDM, SBS elastomer, polyamide, polycarbonate, PET resin, cross-linked polyethylene, copolymer of ethylene and vinyl alcohol, polystyrene, poly-1 ester The polymer blend of claim 16, selected from the group consisting of: polyacrylonitrile homopolymer, polyacrylonitrile copolymer, thermoplastic polyamide, polyacetal, polyvinylidene fluoride, polyethylene glycol, polyisobutylene, and combinations thereof. The additive comprises an elastomer prepared by polymerizing propylene and ethylene in the presence of a chiral metallocene catalyst using an activator and optionally a scavenger, wherein the average propylene content of the elastomer is from about 68% to about 17. The polymer blend of claim 16, which is 92%. 17. The polymer blend of claim 16, wherein the additive comprises a semicrystalline propylene copolymer:
A. A heat of fusion of about 0.5 J / g to about 25 J / g,
B. A crystallinity of about 0.25% to about 15%,
C. A single broad melting point of about 25 ° C. to about 75 ° C.,
D. A weight average molecular weight of 10,000 to 5,000,000 g / cc,
E. MWD (Mw / Mn) is 1.5 to 40.0 and / or F.I. A polymer blend having a Mooney viscosity ML (1 + 4) at 125 ° C. of less than 100. The additive includes a rubber reinforcing composition, and the rubber is an ethylene propylene rubber, an ethylene propylene diene monomer rubber, a neoprene rubber, and / or a styrenic block copolymer rubber, and the rubber is rich in functional amorphous syndiotactic. The polymer blend of claim 16 which is a discontinuous phase within a continuous phase comprising polyolefin. 17. The polymer blend of claim 16, wherein the additive comprises a random copolymer produced by copolymerizing propylene and ethylene in a single reactor process, the random copolymer comprising from about 3 to about 17 mole percent ethylene. The additive comprises a random copolymer having a narrow composition distribution, and 75% by weight of the random copolymer in the immediately preceding or immediately preceding fraction as one or two adjacent soluble fractions, as determined by hot fractionation in saturated hydrocarbons. 17. The polymer blend of claim 16, isolated from the remaining polymer. [Mmmm] pentad having an isotacticity of 25-60% due to a statistical distribution of stereoscopic image errors in the polymer chain, wherein the additive comprises a functional polymer containing a linear isotactic polymer containing a C2-C20 olefin Having a concentration, a weight average molecular weight of 100,000 to 800,000 g / mol, a glass transition temperature of −50 to 30 ° C., a [rmrm] pentad concentration of up to 2.5% of the total pentad region, [rrrr The polymer blend of claim 16, wherein when combined, the [rrrm] pentad concentration is greater than the [rmrm] pentad concentration and is essentially soluble in toluene at 20-80 ° C. Additives are aliphatic hydrocarbon resin, aromatic modified aliphatic hydrocarbon resin, hydrogenated polycyclopentadiene resin, polycyclopentadiene resin, gum rosin, gum rosin ester, wood rosin, wood rosin ester, tall oil rosin, tall oil rosin Ester, polyterpene, aromatic modified polyterpene, terpene phenol, aromatic modified hydrogenated polycyclopentadiene resin, hydrogenated aliphatic resin, hydrogenated aliphatic aromatic resin, hydrogenated terpene and modified terpene, hydrogenated 17. The polymer blend of claim 16, comprising a tackifier selected from the group consisting of rosin acid and hydrogenated rosin ester. The polymer blend of claim 16, wherein the additive comprises a cross-linking agent selected from the group consisting of alcohols, multiols, amines, diamines and triamines. Additives are polar wax, nonpolar wax, polypropylene wax, polyethylene wax, Fischer-Tropsch wax, oxidized Fischer-Tropsch wax, hydroxy stearamide wax, functionalized wax, amorphous wax, carnauba wax, caster oil wax, micro Crystalline wax, beeswax, carnauba wax, castor wax, whale wax, plant wax, candelilla wax, Japanese wax, ouricury wax, Douglas fir bark wax, rice bran wax, jojoba wax, bayberry wax, montan wax, peat wax, ozoke Light wax, ceresin wax, petroleum wax, paraffin wax, polyethylene wax, chemically modified hydrocarbon wax, substituted amide wax Box, and / or derivatives thereof, the polymer blend of claim 16. The polymer blend of claim 16 wherein the additive comprises a crystallization aid. 17. The polymer blend of claim 16, comprising from 10 to 90% by weight additive based on the weight of the polymer blend. An organic clay in which the additive is present in the blend at 0.1 to 50% by weight based on the total weight of the blend, the organoclay being montmorillonite, sodium montmorillonite, calcium montmorillonite, magnesium montmorillonite, nontronite, beidellite, vorcon Scorite, laponite, hectorite, saponite, sauconite, magadite, kenyaite, sobockite, svinordite, stevensite, vermiculite, halloysite, aluminate oxide, hydrotalcite, illite, rectolite, tarsosite, rediteite, fluorine The polymer blend of claim 16 selected from the group consisting of mica and combinations thereof. 17. The polymer blend of claim 16, wherein the polymer blend is a masterbatch that produces a concentrate comprising 10-90 wt% polymer blend melt blended with at least one additive under high shear conditions. A polyolefin rich in amorphous syndiotactic functionalized with functional groups;
Before the functionalized polyolefin comprising the amorphous syndiotactic rich include the following: alpha-olefins of from about 50 wt% or more of C ₃ -C _40, based on the total number of r and m dyads present in the polymer From about 50% to about 80% r dyad; heat of fusion of 10 J / g or less according to the procedure described in ASTM E 794-85; and ash content of 1% by weight or less. 32. The polymer of claim 31 having at least about 6.25% r pentad to about 31.6% r pentad based on the total number of r and m pentads present in the polymer. 32. The polymer of claim 31, comprising about 50% by weight or more of propylene. 32. The polymer of claim 31, further comprising at least 0.5 wt% ethylene, based on the total weight of the polymer. 32. The polymer of claim 31, wherein the heat of fusion is not detectable. 32. The polymer of claim 31, wherein the ash content is 0.1% by weight or less. 32. The polymer of claim 31, wherein the melt flow rate is 0.2 g / 10 min or greater. 32. The polymer of claim 31, wherein based on the total weight of polymer present, at least about 95% by weight of the polymer is soluble in hexane, cyclohexane, xylene or toluene at 25 ° C. 32. The polymer of claim 31, having a weight average molecular weight (Mw) of about 5000 to about 5,000,000 g / mol. 32. The polymer of claim 31, wherein the number average molecular weight (Mn) is from about 5,000 to about 3,000,000 g / mol. 32. The polymer of claim 31, wherein the z-average molecular weight (Mz) is from about 5,000 to about 10,000,000 g / mol. 32. The polymer of claim 31, having no discernable crystallization temperature (Tc). 32. The polymer of claim 31, wherein the functional group comprises a compound having a weight average molecular weight of 1000 or less and comprising a carbon-carbon double bond, a carbon-carbon triple bond, and / or a heteroatom. 32. The polymer of claim 31, wherein the functional group comprises B, N, O, Si, P, F, Cl, Br, I, S, or combinations thereof. The functional group is an aromatic compound, vinyl compound, organic acid, organic amide, organic amine, organic ester, organic diester, organic imide, organic anhydride, organic alcohol, organic acid halide, organic peroxide, and / or these 32. The polymer of claim 31 which is a salt of The functional group is maleic anhydride, citraconic anhydride, 2-methylmaleic anhydride, 2-chloromaleic anhydride, 2,3-dimethylmaleic anhydride, bicyclo [2,2,1] -5-heptene-2, 3-dicarboxylic anhydride, 4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, crotonic acid, bicyclo ( 2.2.2) Oct-5-ene-2,3-dicarboxylic acid anhydride, 1,2,3,4,5, & 6, -octahydronaphthalene-2,3-dicarboxylic acid anhydride, 2-oxa -1,3-diketospiro (4.4) non-7-ene, bicyclo (2.2.1) hept-5-ene-2,3-dicarboxylic anhydride, maleopimaric acid (maleopimaric) acid), tetrahydrophthalic acid anhydride, norborn-5-ene-2,3-dicarboxylic acid anhydride, nadic acid anhydride, methyl nadic acid anhydride, hymic acid anhydride, methyl hymic acid anhydride, x-methyl-bicyclo ( 2.2.1) Hept-5-ene-2,3-dicarboxylic anhydride, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, vinyltrichlorosilane, vinyltris 32. The polymer of claim 31, which is (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane monovinylsilane, monoallylsilane, vinyl chloride or vinylidene chloride. 32. The polymer of claim 31, wherein the functional groups are present in a polyolefin rich in functional amorphous syndiotactic at 1-5% by weight, based on the total weight of the functional polyolefin. 32. The polymer of claim 31, wherein the functionalized amorphous syndiotactic rich polyolefin is heat stable. Functional amorphous syndiotactic rich polyolefin is maleic anhydride grafted functional amorphous syndiotactic rich polypropylene, maleic anhydride rich in functional amorphous syndiotactic rich polypropylene weight 32. The polymer of claim 31 present in a concentration of about 0.005 to 10% by weight maleic anhydride in a polypropylene rich in functional syndiotactic based on The polypropylene rich in functional amorphous syndiotactic contains less than about 1000 ppm free acid groups based on the total weight of the polypropylene and the polypropylene rich in functional amorphous syndiotactic is the total weight of the polypropylene. 50. The polymer of claim 49, comprising less than about 100 ppm phosphite based on Polymer blend containing:
Amorphous syndiotactic rich polyolefins functionalized with functional groups; prior to functionalization, the amorphous syndiotactic rich polyolefins include: about 50 wt% or more of C ₃ ~ From about 50% to about 80% r dyad, based on the total number of r and m dyads present in the polymer, alpha olefin of C ₄₀ ; heat of fusion of 10 J / g or less; and ash content of 1 wt% or less; and C2-C40 polymer, C2-C40 copolymer, elastomer, random copolymer, impact copolymer, fractional polymer, tackifier, crosslinking agent, antioxidant, neutralizing agent, nucleating agent, filler, adhesion promoter, oil content, plastic Agent, wax, ester polymer, rubber reinforcing composition, recycled polymer, blocking agent, antiblocking agent, pigment, dyeing , Processing aids, UV stabilizers agents, lubricants, adjuvants, surfactants, color masterbatches, flow improvers, crystallization aids, or at least one additive comprising a combination thereof. A functional amorphous syndiotactic rich polyolefin is an amorphous syndiotactic rich polypropylene grafted with maleic anhydride, maleic anhydride is functional in the functional syndiotactic rich polypropylene 52. The polymer of claim 51, present at a concentration of about 0.005 to 10% by weight maleic anhydride, based on the weight of the amorphous syndiotactic rich polypropylene. Additives are homopolypropylene, propylene copolymerized with up to 50% by weight of ethylene or C4 to C20 α-olefin, isotactic polypropylene, random copolymer of propylene and ethylene, random copolymer of polypropylene and butene or hexene, polybutene , ethylene vinyl acetate, a density 0.915~0.935g / cm ³ or less of polyethylene, linear polyethylene, density 0.86~0.90g / cm ³ or less of polyethylene, density 0.90~0.915g / cm ³ The following polyethylene, polyethylene having a density of 0.935 to 0.945 g / cm ³ or less, polyethylene having a density of 0.945 to 0.98 g / cm ³ or less, ethylene methyl acrylate, copolymer of acrylic acid, polymethyl methacrylic acid, polyvinyl chloride , Polybutene-1, isotactic polybutene, ABS resin, ethylene-propylene rubber, sulfurized EPR, EPDM, SBS elastomer, polyamide, polycarbonate, PET resin, cross-linked polyethylene, copolymer of ethylene and vinyl alcohol, polystyrene, poly-1 ester 52. The polymer blend of claim 51, selected from the group consisting of: polyacrylonitrile homopolymer, polyacrylonitrile copolymer, thermoplastic polyamide, polyacetal, polyvinylidene fluoride, polyethylene glycol, polyisobutylene, and combinations thereof. 52. The polymer blend of claim 51, wherein the additive comprises a semicrystalline propylene copolymer:
A. A heat of fusion of about 0.5 J / g to about 25 J / g,
B. A crystallinity of about 0.25% to about 15%,
C. A single broad melting point of about 25 ° C. to about 75 ° C.,
D. A weight average molecular weight of 10,000 to 5,000,000 g / cc,
E. MWD (Mw / Mn) is 1.5 to 40.0 and / or F.I. A polymer blend having a Mooney viscosity ML (1 + 4) at 125 ° C. of less than 100. The additive comprises a random copolymer produced by copolymerizing propylene and ethylene in a single reactor process, the random copolymer comprising from about 3 to about 17 mole percent ethylene, and the random copolymer having a narrow composition 75% by weight of a random copolymer is isolated from the remaining polymer in the immediately following or immediately preceding fraction as a 1 or 2 adjacent soluble fraction, as determined by thermal fractionation in saturated hydrocarbons 52. The polymer blend of claim 51. Additives are aliphatic hydrocarbon resin, aromatic modified aliphatic hydrocarbon resin, hydrogenated polycyclopentadiene resin, polycyclopentadiene resin, gum rosin, gum rosin ester, wood rosin, wood rosin ester, tall oil rosin, tall oil Rosin ester, polyterpene, aromatic modified polyterpene, terpene phenol, aromatic modified hydrogenated polycyclopentadiene resin, hydrogenated aliphatic resin, hydrogenated aliphatic aromatic resin, hydrogenated terpene and modified terpene, hydrogenated 52. The polymer blend of claim 51, comprising a tackifier selected from the group consisting of a fluorinated rosin acid and a hydrogenated rosin ester. 52. The polymer blend of claim 51, comprising from 10 to 90% by weight additive, based on the weight of the polymer blend. Polyolefins including amorphous syndiotactic rich, a contact product of a functional group, and functionalized catalysts, polyolefins containing the amorphous syndiotactic rich contains the following: about 50% or more by weight of C ₃ -C ₄₀ α-olefin, about 50% to about 80% r dyad based on the total number of r and m dyads present in the polymer, heat of fusion of 10 J / g or less, and ash content of 1 wt% or less. 59. The contact product of claim 58, wherein the functionalized catalyst is an organic peroxide. Functionalized catalyst is benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, t-butylperoxyisopropyl carbonate, di-ti-butyl perphthalate, 2,5-dimethyl-2,5-di (t-butylperoxy) hexene 2,5-dimethyl-2,5-di (t-butylperoxy) hexene-3, di-t-butyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, dilauryl peroxide, dicumyl peroxide and combinations thereof 59. The contact product of claim 58, selected from the group consisting of: 59. The contact product of claim 58, wherein the functional group comprises a compound having a weight average molecular weight of 1000 or less and comprising a carbon-carbon double bond, a carbon-carbon triple bond, and / or a heteroatom. 59. The contact product of claim 58, wherein the functional group comprises B, N, O, Si, P, F, Cl, Br, I, S, or combinations thereof. The functional group is an aromatic compound, vinyl compound, organic acid, organic amide, organic amine, organic ester, organic diester, organic imide, organic anhydride, organic alcohol, organic acid halide, organic peroxide, and / or these 59. The contact product of claim 58, wherein The functional group is maleic anhydride, citraconic anhydride, 2-methylmaleic anhydride, 2-chloromaleic anhydride, 2,3-dimethylmaleic anhydride, bicyclo [2,2,1] -5-heptene-2, 3-dicarboxylic anhydride, 4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, crotonic acid, bicyclo ( 2.2.2) Oct-5-ene-2,3-dicarboxylic acid anhydride, 1,2,3,4,5, & 6, -octahydronaphthalene-2,3-dicarboxylic acid anhydride, 2-oxa -1,3-diketospiro (4.4) non-7-ene, bicyclo (2.2.1) hept-5-ene-2,3-dicarboxylic acid anhydride, nadonic acid anhydride, methyl nadic acid anhydride, Anhydrous Mic acid, methylhymic anhydride, x-methyl-bicyclo (2.2.1) hept-5-ene-2,3-dicarboxylic anhydride, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid Methyl, ethyl methacrylate, butyl methacrylate, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane monovinylsilane, monoallylsilane, vinyl chloride or 59. The contact product of claim 58, which is vinylidene chloride. 59. The contact product of claim 58, wherein the functional groups are present in the contact product from 0.005 to 99% by weight, based on the total weight of the contact product. 59. The contact product of claim 58, wherein the functional group is present in the contact product at 1 to 5 wt%, based on the total weight of the contact product. 59. The contact product of claim 58, wherein the contact product is heat stable. The functionalized amorphous syndiotactic rich polyolefin is an amorphous syndiotactic rich polypropylene, the functional group is maleic anhydride, and the maleic anhydride has a concentration of about 0, based on the weight of the contact product. 59. The contact product of claim 58, present in the contact product at 0.005 to 10 wt% maleic anhydride. The amorphous syndiotactic rich polyolefin is amorphous syndiotactic rich polypropylene, the functional group is maleic anhydride, and the contact product is less than about 1000 ppm free acid based on the total weight of the contact product 59. The contact product of claim 58 comprising a group. The amorphous syndiotactic rich polyolefin is an amorphous syndiotactic rich polypropylene, the functional group is maleic anhydride, and the contact product is less than about 100 ppm phosphorus based on the total weight of the contact product. 59. The contact product of claim 58, comprising an acid salt. Polymer containing amorphous syndiotactic rich polypropylene functionalized with maleic anhydride, wherein the functional polypropylene is from about 50% to about 80, based on the total number of r and m dyads present in the polymer. A polymer comprising the following r dyad, having a heat of fusion of 10 J / g or less and an ash content of 1 wt% or less. 72. The polymer of claim 71, having at least about 6.25% r pentad to about 31.6% r pentad based on the total number of r and m pentads present in the polymer. 72. The polymer of claim 71, further comprising at least 0.5 wt% ethylene, based on the total weight of the polymer. 72. The polymer of claim 71, wherein the heat of fusion is not detectable. 72. The polymer of claim 71, wherein the ash content is 0.1 wt% or less. 72. The polymer of claim 71, wherein the melt flow rate is 0.2 g / 10 min or greater. 72. The polymer of claim 71, wherein at least about 95% by weight of the polymer is soluble in hexane, cyclohexane, xylene or toluene at 25 [deg.] C, based on the total weight of polymer present. 72. The polymer of claim 71, wherein the weight average molecular weight (Mw) is from about 5000 to about 5,000,000 g / mol. 72. The polymer of claim 71, wherein the number average molecular weight (Mn) is from about 5,000 to about 3,000,000 g / mol. 72. The polymer of claim 71, wherein the z-average molecular weight (Mz) is from about 5,000 to about 10,000,000 g / mol. 72. The polymer of claim 71, having no discernable crystallization temperature (Tc). 72. The polymer of claim 71, wherein maleic anhydride is present in the polymer at from 0.005 to 10% by weight, based on the total weight of the polymer. 72. The polymer of claim 71, wherein the polymer is heat stable. Polypropylene rich in amorphous syndiotactic functionalized with maleic anhydride and a polymer blend comprising at least one additive, based on the total number of r and m dyads in which the functional polypropylene is present in the polymer. From about 50% to about 80% r dyad; heat of fusion up to 10 J / g; and ash content up to 1% by weight, and the additive is a C2-C40 polymer, elastomer, random copolymer, impact copolymer, Fractional polymer, tackifier, crosslinking agent, antioxidant, neutralizing agent, nucleating agent, filler, adhesion promoter, oil, plasticizer, wax, ester polymer, blocking agent, blocking agent, pigment, dye, Processing aids, UV stabilizers, lubricants, adjuvants, surfactants, color master batches, fluidity improvers, binders Kasukezai, and is selected from the group consisting of polymer blends. 85. The polymer blend of claim 84, comprising from 10 to 90% by weight additive, based on the weight of the polymer blend. Amorphous syndiotactic rich polyolefin, functional group functionalized amorphous syndiotactic rich polyolefin, or an adhesive composition comprising a combination thereof, the amorphous syndiotactic rich Polyolefins include: about 50% by weight or more C ₃ -C ₄₀ alpha olefins, about 50% to about 80% r dyads based on the total number of r and m dyads present in the polymer; 10 J / g or less; and if the ash content is 1 wt% or less and the functional group is present, the weight average molecular weight is 1000 or less, a carbon-carbon double bond, a carbon-carbon triple bond, and / or A compound containing a heteroatom; the adhesive composition has a peel strength relative to isotactic polypropylene of about And a .5lb / in or greater, peel strength to the polyester film is about 0.5 lb / in or more. C2-C40 polymer, C2-C40 copolymer, elastomer, random copolymer, impact copolymer, fractional polymer, tackifier, crosslinking agent, antioxidant, neutralizing agent, nucleating agent, filler, adhesion promoter, oil content, plastic Agent, wax, ester polymer, rubber reinforcing composition, recycled polymer, blocking agent, antiblocking agent, pigment, dye, processing aid, UV stabilizer, lubricant, adjuvant, surfactant, color masterbatch, flow 87. The adhesive composition of claim 86, further comprising at least one additive selected from the group consisting of a property improver, a crystallization aid, and combinations thereof. 87. The adhesive composition of claim 86, wherein at least about 95% by weight of the adhesive is soluble in hexane, cyclohexane, xylene, or toluene at 25 [deg.] C, based on the total weight of adhesive present. 87. The adhesive composition of claim 86, wherein the polyolefin comprises about 60% or more propylene. 87. The adhesive composition of claim 86, wherein the polyolefin comprises at least 0.5 wt% ethylene, based on the total weight of the polyolefin. 90. The adhesive composition of claim 86, wherein the heat of fusion of the polyolefin is not detectable. 90. The adhesive composition of claim 86, wherein the polyolefin comprises an ash content of 0.1% by weight or less. Aliphatic hydrocarbon resin, aromatic modified aliphatic hydrocarbon resin, hydrogenated polycyclopentadiene resin, polycyclopentadiene resin, gum rosin, gum rosin ester, wood rosin, wood rosin ester, tall oil rosin, tall oil rosin ester, polyterpene , Aromatic modified polyterpenes, terpene phenols, aromatic modified hydrogenated polycyclopentadiene resins, hydrogenated aliphatic resins, hydrogenated aliphatic aromatic resins, hydrogenated terpenes and modified terpenes, hydrogenated rosin acids, 87. The adhesive composition of claim 86, further comprising one or more tackifiers selected from the group consisting of hydrogenated rosin esters, derivatives thereof, and combinations thereof. The adhesive further comprises polar wax, nonpolar wax, Fischer-Tropsch wax, oxidized Fischer-Tropsch wax, hydroxy stearamide wax, functionalized wax, polypropylene wax, polyethylene wax, wax modifier, and combinations thereof 90. The adhesive composition of claim 86, comprising one or more waxes selected from the group. The adhesive further comprises plasticizers, oils, stabilizers, antioxidants, pigments, dyes, polymer additives, defoamers, preservatives, thickeners, flow improvers, humectants, fillers and water. 90. The adhesive composition of claim 86, comprising one or more additives selected from the group consisting of: The adhesive composition of claim 86, wherein the fixing time is 30 seconds or less. A consumer product, manufactured product, packaging adhesive, packaging, disposable product, film, pressure sensitive adhesive, laminate product, textile product, hot melt adhesive, carpet, tape, comprising the adhesive composition of claim 1. Includes roofing sheets, roofing members, reflective materials, woodworking technology materials, consumer materials, labels, bookbinding materials, road surface display compositions, sealing compositions, pavement compositions, stick glues, pipes, clothing materials, transparent glazing Material, or a combination of these. The functionalized amorphous syndiotactic functionality a rich polyolefin, polyolefins containing the functionalized amorphous syndiotactic rich include: about 50 wt% or more of C ₃ -C ₄₀ alpha-olefin About 50% to about 80% or less of the r dyad based on the total number of r and m dyads present in the polymer; and a heat of fusion of 10 J / g or less. A method for producing a polymeric material comprising:
Melt-blending the amorphous syndiotactic rich polyolefin and at least one additive under high shear conditions to produce a concentrate comprising 10-90 wt% polyolefin, and then the concentrate It blended with at least one other substance, wherein the step of generating the final product, wherein the polyolefin amorphous syndiotactic rich comprises a C ₃ -C ₄₀ alpha-olefin of at least about 50 wt%, A process wherein the r dyad is about 50% to about 80% or less based on the total number of r and m dyads present in the polyolefin; and the heat of fusion is 10 J / g or less; and the ash content is 1% by weight or less. A polyolefin rich in amorphous syndiotactic is functionalized with functional groups, the functional groups having a weight average molecular weight of 1000 or less, carbon-carbon double bonds, carbon-carbon triple bonds, and / or heterogeneous 100. The method of claim 99, comprising a compound comprising an atom. 101. The method of claim 100, wherein the functionalized amorphous syndiotactic rich polyolefin is an amorphous syndiotactic rich polypropylene functionalized with maleic anhydride. 102. The method of claim 101, wherein the amorphous syndiotactic rich polyolefin is functionalized simultaneously with the formation of the concentrate. A method of producing a polyolefin rich in functional amorphous syndiotactic comprising the following steps:
A. Adding an olefin monomer, a metallocene catalyst, and an activator into the aliphatic solvent of the reactor;
B. Performing a catalyst solution polymerization of the olefin monomer in the reactor to produce a polyolefin rich in amorphous syndiotactic;
C. Removing the monomer to remove unreacted olefin monomer;
D. Mixing the amorphous syndiotactic rich polyolefin, functional group and free radical initiator in the aliphatic solvent at a temperature and for a time sufficient to produce the functional amorphous syndiotactic rich polyolefin. Performing a solvent-based functionalization comprising: E. Removing the aliphatic solvent;
Here, polyolefins including amorphous syndiotactic rich includes C ₃ -C ₄₀ alpha-olefin of at least about 50 wt%; about 50% based on the total number of r and m dyads present in the polyolefin to about It has an r dyad of 80% or less; a heat of fusion of 10 J / g or less; and an ash content of 1% by weight or less. 104. The method of claim 103, wherein the functionalized amorphous syndiotactic rich polyolefin is an amorphous syndiotactic rich polypropylene functionalized with maleic anhydride. 104. The method of claim 103, further comprising an organoclay addition after the solvent-based functionalization step D. A method of producing a polyolefin rich in functional amorphous syndiotactic comprising the following steps:
A. Adding a melt containing a polyolefin rich in amorphous syndiotactic, functional groups, and a free radical initiator to a mixing device;
B. Contacting the lysate in the mixing apparatus at a temperature and for a time sufficient to produce a polyolefin rich in the functional amorphous syndiotactic, wherein the amorphous syndiotactic rich About 50% by weight or more of C ₃ -C ₄₀ α olefins; about 50% to about 80% or less r dyads based on the total number of r and m dyads present in the polyolefin; melting of 10 J / g or less Heat; and an ash content of 1% by weight or less. 107. The method of claim 106, wherein the functionalized amorphous syndiotactic rich polyolefin is an amorphous syndiotactic rich polypropylene functionalized with maleic anhydride. 107. The method of claim 106, further comprising the addition of organoclay after said contacting step B.