TW200406456A - Heteromorphic polymer compositions and a process for preparing the same and the hot melt adhesive formulation comprising the same II - Google Patents

Abstract

The subject invention pertains to heteromorphic polymer compositions characterized as comprising comprising: (a) a homogeneous linear or substantially linear ethylene/α -olefin interpolymer backbone; and (b) a branch appending from the backbone, which branch comprises an ethylene homopolymer or ethylene/α-olefin interpolymer having a density which is at least 0.004 g/cm3 greater than that of the backbone. At least one of the backbone polymer or the branch polymer may be optionally functionalized to promote adhesion to polar surfaces. The heteromorphic polymer compositions of the invention exhibit enhanced upper service temperature. Also disclosed is a process for preparing the heteromorphic polymer compositions of the invention.

Description

200406456 发明, Description of invention L Technical field to which the invention belongs 3 The present invention relates to a polymorphic olefin polymer, and in particular, the present invention relates to a homogeneously branched linear or substantially linear ethylene / α-olefin 5 interpolymer The main chain, and a high-density ethylene copolymer or a long chain branch of an ethene / α-olefin interpolymer, is a dilute hydrocarbon polymer attached to the interpolymer main chain. L iltr Homogeneous ethylene / α-olefin interpolymer is characterized by a narrow molecular weight distribution and a narrow short-chain branch distribution. In addition, homogeneous ethylene 10 interpolymers containing long chain branches, referred to as "homogeneous linear" ethylene polymers, are indicated and declared in U.S. 5,272,236 and U.S. 5,278,272. The loss of low molecular weight, wax content and the ability to evenly distribute the comonomers makes it possible for manufacturers to make elastomers such as ethylene / propylene, ethylene / butene, and acetoin / sintein elastomers. However, if the homogeneous linear and substantially linear ethylene polymers lack heterogeneous branched polyethylene (and hence high crystalline melting peaks) with high linearity ratio characteristics, homogeneous linear and substantially linear ethylene polymers tend to have a poorer High temperature resistance, especially when the polymer density is less than 0.920 g / cm3, less than the heterogeneous branched polymer of the same density. For example, homogeneous linear and substantially linear elastomers lose their strength at 60 ° C or less. 20 This is due to the fact that the low-density polymer has a molecular structure characterized by the appearance of edged micelles and typically lacks a high-dazzling point laminated structure. When this different system is less obvious, there is even a higher density homogeneous linear and substantially linear acetal polymer with a bonded structure, which is usually melted at a temperature lower than that of its heterogeneous branch 200406456. Regardless of its polymerization catalyst, polyethylene faces a practical limit of use beyond its crystalline melting point, which does not exceed about 140 ° C. By mixing high crystallinity polyethylene with low crystal elasticity, it is possible to increase the operating temperature of the elasticity. However, larger improvements in high-resistance lines are needed. In addition, in general, however, as the amount of high-density fraction increases, the high-temperature resistance increases, and as this rate increases (therefore, the elastic properties, in a linear or substantially linear line with a density less than 0.9900 g / cm3 In the case of vinyl polymers, the number of defects is reduced). In Example 3 mixed with a homogeneous linear and substantially linear ethylene polymer having a density greater than 0.900 g / cm3, when the high-density 10 fraction was increased, the high-temperature resistance was increased, and the tear resistance and impact resistance were poorly reduced. . U.S. Patent No. 5,350,072 indicates polymers exhibiting formation to join a long chain branch of a linear polyethylene with a free radical starter by itself. When the self-bonding is used to increase the molecular weight of polyethylene and improve the melting power, it does not affect the crystallinity of the polyethylene, and therefore does not affect the high temperature resistance of the polyethylene. U.S. Patent No. 5,346,936 indicates a substantially linear ethylene polymer for joint modification, which does not necessarily need to be mixed with thermoplastic compounds, such as high density polyethylene, linear low density polyethylene, and low density polyethylene. 20 The industry will find the advantages of elastomers with enhanced high temperature performance without sacrificing coefficient and / or tear resistance and impact resistance. The enhanced high temperature performance shows advantages, for example, it is better for the sole to endure the heat of the clothes dryer. In another specific embodiment, the pressure sensitive adhesive 7 200406456 发明, description of the invention exhibits reduced spread resistance. As used herein, the term "polymer" means a compound made from polymerized monomers, whether of the same or different type. This class of polymers therefore includes the term "simple polymer" and is generally used to refer to polymers prepared from only one comonomer, and the term "interpolymer" is defined below. The term "interpolymer" means a polymer prepared by the polymerization of at least two different types of comonomers. The term "interpolymer" thus includes the term "copolymer", which is generally used to refer to polymers prepared from two comonomers and polymers prepared from more than two different types of comonomers. [Summary of the Invention] A unique polymer composition of the present invention includes: (A) —a homogeneous linear or substantially linear ethylene / α-olefin interpolymer main chain; and (B) —ethylene simple polymer or ethylene / α-olefin interpolymer attached to the main chain of the interpolymer and having a density of at least 0.0004 g / cm3 larger than the first interpolymer main chain. The 15 polymer composition is more resistant to deformation at a higher temperature than a relatively physical mixing of the first and second interpolymers or a mixing in the reactor. The improved high-temperature performance is reflected in higher processing temperature (ULST) values under load, that is, the identity of the polymorphic polymer composition is lost due to softening / melting, as measured using a Rheometrics Solids Analyzer Use the setting of 20 or lower. When you do not want to be subject to the theoretical rate, it is generally believed that the materials and scientific laws used to improve the high temperature resistance of homogeneous or substantially linear elastomers are illustrated in Figure 1. As shown in Fig. 1, the elastic object is a soft part to provide polymorphic polymorphic polymer. 200406456 玖, description of the invention The elasticity of the composition at room temperature. Joining a hard part, such as high-density polyethylene, which has a higher crystalline melting point, improves the ULST because the hard parts co-crystallize to the small scattering areas they have and as a combination of the elastomeric chain to a three-degree spatial network . 5 According to the composition of the branched polymer and the method of branching, the branch will have many types, and some basic types are shown in Figure 2, and Figure 2-1 shows a substantially linear copolymer main chain different from three Type polymer branch type. Figure 2-l (a) illustrates the branching caused by an "H-link" with the main chain polymer. This may, for example, be introduced to arbitrarily cross-link the backbone polymer and the 10 precursor polymer to the polymorphic long chain branch. Figure 21- (b) shows a long chain branch attached to the main chain polymer at (two or more) positions. If the long-chain branch can still co-crystallize or form a "hard" phase that improves the polymer's temperature resistance and / or physical properties, the method introduced by this long-chain branch is acceptable and within our definition of long-chain branch Within range. Figure 2-l (c) illustrates the formation of a "T" and 15 backbone polymer. This can be caused, for example, by joining a reactive terminal group of a polymorphic long-chain branched precursor polymer with the main chain polymer, or can be a reactive terminal group such as vinyl and comonomers in the main chain polymer. Formed by copolymerization of the polymerization reaction (in this example, the "backbone polymer" is only an idea and does not appear to be substantially pure). 20 Figure 2-2 shows an example of an exemplary variation. One of the linear copolymers (2-2) has a main chain polymer with a "T" type polymorphic long-chain branch such as caused by a copolymerization reaction or joining a terminal family. The ethylene / α-olefin interpolymer (A), which contains the polymorphic form 9 200406456 of the invention, the main chain of the olefin polymer described in the invention, will be a homogeneous linear or substantially linear ethylene / α-olefin interpolymer Both are described in more detail below. The density of the backbone polymer depends on the type and amount of comonomer used. Density can be controlled according to methods familiar to those skilled in the art to control the softness of the polymer in this range from highly amorphous, highly elastic, highly crystalline, and inelastic. The choice of backbone polymer density will be based on the requirements of each application based on performance requirements familiar to those skilled in the art. Typically, however, the density of the backbone polymer will be less than 0.920 g / cm3, preferably less than 0.900 g / cm3, and more preferably less than 0.880 g / cm3. The best elastic properties in application are required. The density of the main chain polymer will be less than 0.870 g / cm3, more preferably less than 0.865 g / cm3, and it can be achieved with a density as low as 0.850 g / cm3. The molecular weight of the main chain polymer can be similarly changed for each system. When a branched polymer is attached to the main chain polymer for cross-linking or joining, it is preferable to reduce the molecular weight of the main chain polymer to reduce the coagulation system, especially if the branched poly 15 compound is of high molecular weight or at a reaction position of Multifunctional. Tricor's physical properties can even enable rather low-molecular-weight backbone polymers to have optimized connectivity due to the polymorphic nature of the composition of this invention, which is one aspect of this invention. Therefore, it is possible to obtain good physical properties and good handling properties at the same time. Typically, however, the main chain polymer will have a melt index (12) from 0.01 to 10,000 g / min, and preferably from 0.01 to l 10,000g / 10min. A particularly good dissolution index is greater than 10 g / 10 min, and more preferably greater than 20 g / 10 min. Note that for low-molecular-weight polymers, that is, a polymer with a melt index greater than 1,000 g / lOmin 10 200406456 玖, invention description, the molecular weight can be indicated to measure the polymer's melt viscosity at 350 ° F. Polymers with dazzling indices of 1,000 g / 10 min and 10,000 g / min have a melt viscosity of 350 ° F. The techniques set by the Test Procedures in the following paragraphs are measured at approximately 8,200 and 600 centipoise. 5 The branch polymer (B), which is attached to the polymer backbone (A), can be any polymer that can be copolymerized with a comonomer during the manufacture of the backbone polymer, or it can be copolymerized with the backbone polymer Join or cross-link, and it has a density of at least 0.004 g / cm3, preferably at least 0.0068 g / cm3, and more preferably at least 0.01 g / cm3, which is greater than the density of the main chain compact. Preferably, the branched polymer (B), in its pure state, will have a glass transition (Tg) or crystalline melting point (Tm) of at least 10 ° C, preferably 20 ° C, and most preferably At least 50 ° C is higher than the Tg or Tm of the backbone polymer in the pure state (ie higher than it). Note that for the purposes of this invention, the solution "joining" means connecting a terminal family of the branched polymer to the main chain polymer, and the term "cross-linking" means, in a limited form, via one or more 15 Extend the connection of the long-chain branch precursors to form a polymorphic long-chain branch composition rather than a cross-bond network. Non-limiting examples of polymorphic long-chain branched materials include heterogeneous and homogeneous branched linear ethylene monomers and ethylene / α-olefin interpolymers, and substantially linear ethylene monomers and ethylene / α-olefin interpolymers, Each will be described in more detail below. This branched polymer may be more functional, not necessarily. A suitable branched polymer for one backbone polymer may not be suitable for another backbone polymer. For example, a suitable branched polymer with a homogeneous linear or substantially linear ethylene / octane interpolymer with a density of 0.865 g / cm3 would be 11 33: 200406456. The invention description has a density of 0.900 g / cm3. An ethylene / octene interpolymer. However, the same branched polymer is not suitable for use in combination with a polymer backbone having a homogeneous linear or substantially linear ethylene / octene interpolymer with a density of 0.920 g / cm3, where the Tm of the former is not less than 10 ° C is greater than the latter at Tm (in fact, it is significantly lower than 5). The polymorphic long chain branch will have a more sufficient molecular weight to co-crystallize or form a phase with other branched polymers or additional polymers. Preferably, the polymorphic long-chain branch will have an average molecular weight (Mw) of at least 1,000, and preferably at least 3,000, such as the method of Test Methods set according to the following paragraph. The amount of backbone polymer should be sufficient to make it a continuous or co-continuous phase in the mix of the backbone polymer and the heterolong-chain branched polymer. In particular, the weight ratio of the main chain polymer to the branched polymer is usually greater than 1: 3, preferably at least 1: 2, and most preferably greater than 1: 1. Those skilled in the art will recognize that the optimal ratio will vary depending on the application and will depend on the properties of the elastomer, above the properties. The average number of polymorphic long chain branches per polymer backbone will be sufficient to provide an improved temperature resistance of the final polymer composition as measured by RSA and an improvement in tension which is greater than that of comparable polymers A simple physical blend is provided with copolymerization, bonding, and cross-linking. Preferably, the 20 composition of the invention will exhibit a temperature resistance as measured by RSA of at least 10 ° C, and preferably at least 15 ° C, which is greater than a physical blend of comparable polymers. Preferably, the composition of the invention exhibits an ultimate tension of at least 70 percent, more preferably at least 85 percent, and more preferably at least 85 percent of the physical mixing of comparable polymers. Description The physical mixing of comparable polymers, etc., or more, can be easily obtained with the ultimate physical mixing of comparable polymers. The average number of polymorphic long chain branches per polymer backbone molecule, however, will not be so great as to reduce the elastic properties of the polymer backbone to an unacceptable level. For example, when the backbone polymer has a With a density of less than 0.900 g / cm3, the composition of the invention will preferably exhibit an elongation percentage of at least 40 percent, more preferably at least 50 percent, and more preferably at least 50 percent. Comparing polymer blends of 60 percent, it is easily achievable to show that the composition has an elongation percentage equal to or beyond that of the comparative blend. 10 The ethylene polymer is used as a polymer main chain (A) and the polymorphic long-chain branch (B) may be an interpolymer of independently ethene and at least one α_dilute hydrocarbon. Suitable α-olefins are represented by the following structural formula: ch2 = chr where R is a hydrocarbon radical. The 15 comonomers forming part of the main chain polymer (A) may be the same or different comonomers forming a polymorphic long chain branch. R usually has from one to twenty carbon atoms. Although suitable as a comonomer for a solution, gas phase or fluid polymerization reaction, suitable alpha-dilute hydrocarbons or mixtures thereof include CrC ^ oa-olefins, styrene, tetrafluoroethylene, ethylfluorenyl, benzene butane 〇, 1,4-dioxane, 1,7-octane, and cyclodilution, such as cyclopentene, cyclohexene, cyclooctene, dicycloheptene (NB), and ethylene bicycloheptene Olefin (ENB). The preferred CVCm a-woene contains 1-propylene, 1-butene, _isobutene, 丨 _ 戍. `` F, Λ-hexene Λ 4 · methyl-1 · pentene, 1-heptene and 1-octene, and other monomers of this type 13 333 · 200406456 发明, invention description. Preferably, the olefin will be kappa butene, pentene, 4 • methyl, 1-pentene, 1-hexene, 1-heptene, octene, NB * ENB, or a mixture thereof. More preferably, the alpha-olefin will be 1-hexene, heptene, bustene, or a mixture thereof. Optimally, the alpha-olefin will be 1-Xinfu. An ethylene / α-enefe / triene terpolymer can also be used as the elastic polymer of the invention. Suitable alpha-olefins include the alpha-olefins described above to suitably make ethylene alpha-olefin copolymers. Diene suitable for the preparation of the monomer of the terpolymer is typically a non-conjugated diene, having from 2 to 15 carbon atoms. Representative examples of suitable non-co-dienes that can be used to prepare the binary polymer include: a) linear non-cyclic diene such as M_hexadiene, i, 5-heptadiene, And 丨, 6-octadiene; b) branched acyclic diene such as 5-methyl 4, 'hexadiene, 3,% dimethyl-1-6 · octadiene, and 3,7 -Dimethyl q, octadiene, and 19-decadiene. 15 C) monocyclic aliphatic cyclic diene such as 4-vinylcyclohexene, 1-allyl isopropylene cyclohexane, 3-allyl cyclopentene, 'allyl cyclohexene, and Isopropenyl-4-butenylcyclohexane. d) Polycyclic aliphatic ring-blocking and bridging diene such as dicyclopentadiene, alkenyl, alkenylene, cycloolefin, and cycloalkylene based bicycloheptene such as methylene bicyclo 0 heptene, 5-methylene Methyl-2-bicycloheptene, 5-methylene-6,6-dimethyl-2-bicycloheptene, 5-propenyl_2_bicycloheptene, 5- (3-cyclopentenyl) _2_ Bicycloheptene, 5-ethylene-2-bicycloheptene, 5-cyclohexylene-2-bicycloheptene, etc. 14 ^ u〇456 发明, description of the invention The preferred diene is selected from the group consisting of! 4 ~ mesh hexamethylene dioxane, dicyclopentafluorene, 5-ethylidene-2-bisthionium diene, 5_methyl_2 · 镳: τ 2 %% diene, 7_methyl -Octadiene, 4-Ethylcyclohexanone, and others who are worried about hearing, or family. A suitable conjugated diene is 1,3-pentadiene. The preferred terpolymers useful for Qian Ming are ethylene, acrylic, and a non-conjugated diene (briber) terpolymer. This terpolymer is commercially available. The homogeneous polyethylene which can be used as the component (A) and rhenium of the present invention is soluble in two broad categories of 'linear homogeneous polyethylene' and substantially linear homogeneous polyethylene. Both are known. Homogeneous | composite ethylene 'is randomly distributed in any of its copolymerized mono-systems-a given interpolymer molecule has substantially all interpolymer molecules having the same ethylene / comonomer ratio in the interpolymer . Homogeneous polymers are usually characterized by a melting peak between -30t: and 150t, which was decided to use a micro 15-scan scanning calorimeter (DSC). The single melting peak was determined by normalizing indium and deionized water using a differential scanning calorimeter. The method includes a sample size of 7mg, a "first heat," to about 18 ° C, which is kept for 4 minutes, a cooling at 10C / min. To -30 ° C, which is kept for 3 minutes, and heated to 1 〇 / 〇 · to 14 ° C for the "second heat". The single melting peak is taken from the "20 second heat" heat flow versus temperature curve. The total heat of polymer fusion is calculated under the curve Area. For a polymer with a density of 0.875g / cm3, the single melting peak can show a…, depending on the sensitivity of the instrument, a “protrusion” or a “peak,” on the low melting side, 15 200406456. Less than 12 percent, typically less than 9 percent, and more typically less than 6 percent of the total heat of the polymer fusion. The artefact can also be found in homogeneous linear polymers such as Exact TM resin (available from Exxon Chemical Company) and the basis for discerning the monotonic change in slope from the melting region of the artifact 5 with a single melt. The artificial device occurs at 34 ° C, typically at 27 ° C, and more typically 20 ° of the melting point of this single melting peak C. Because the fusion heat of an artefact can be determined separately by the integral of the area that is tight in the heat flow versus temperature curve. In addition or in another term, the homogeneity of the polymer is typically described as 10 CDBI ( Composition Distribution Branch Index) and is defined as the weight percentage of a polymer molecule with a comonomer content in the middle of the total mole comonomer content of 50%. The CDBI of a polymer is conveniently calculated from what is known here Technological data such as, for example, the temperature rise release fraction (herein abbreviated as "TREF") are described in, for example, Wild et al, Journal 15 of Polymer Science, Poly. Phys. Ed Vol. 20, p. 441 (1982), in US Patent 5,089,321 (Chum et al.). For homogeneous linear and substantially linear ethylene, the α-olefin polymer used in the invention is preferably greater than one hundred CDBI. 50%, more preferably more than 70%. Homogeneous polymers also have a molecular weight distribution, Mw / Mn, less than or equal to 20 to 3 (when the density of the interpolymer is less than about 0.960g / cm3) , Preferably less than or equal to 2.5. Determination of molecular weight The deduction uses a narrow molecular weight distribution polyethylene standard (from Polymer Laboratories) and its release volume. The SLEP system analysis uses gel permeation chromatography (GPC) in a Waters 150C high temperature color 16 200406456 发明, invention description layer analysis unit device A three-column column with a differential refractometer and mixed holes. This column is provided by Polymer Laboratories and is usually filled with pore sizes ι03, ι04, 105, and 106. Solvent-based 1,2,4-trichlorobenzene was prepared from a sample solution of 0.3% by weight for injection. The flow rate is 1.0 ml / min, the unit operating temperature is 140C, and the injection size is 100 microliters. The equivalent polyethylene molecular weight was determined to use suitable Mark-Houwink coefficients for polyethylene and polystyrene (as described in Williams and Ward in Jorunal of Polymer Science. Polymer Letters, Vol. 6, ρ · 621 1968) to Derive the equation M polyethylene = a · (^ 4 聚 笨 10 u) b. In this equation, a = 0.4316 and b = 1.0, the average molecular weight, Mw, is calculated in a general way by this equation:

Mw = Σ (wiX Mi) where ⑼ and ^ / ^ are respectively the weight fraction and molecular weight released from the i-th item of the GPC column. 15 Homogeneous linear ethylene polymers have been commercially available for a long time. For example, in US Patent No. 4,937,299 to Elston, a homogeneous linear ethylene polymer can be prepared using a general polymerization procedure using a Ziegler-type catalyst such as, for example, a zirconium-vanadium catalyst system, US Patent No. 4,937,299 to Ewen et al. And US · Patent No. 5,218,071 to Tsutsui et al. Discloses the use of metal dicyclopentadiene compound catalysts, such as zirconium and aluminum-based catalyst systems, for the preparation of homogeneous linear ethylene polymers. Homogeneous linear ethylene polymers are typically characterized by a molecular weight distribution, Mw / Mn, about 2. Commercially available examples of homogeneous linear ethylene polymers include those of Mitsui 17 200406456.

Tafmer ™ resins sold by Petrochemical Industries and Exact ™ tree moons by Exxon Chemical Company. A substantially linear ethylene polymer (SLEP) is a homogeneous polymer with long chain branches. They are disclosed in U.S. Patent No. 5,272,236 and 5,278,272. 5 SLEPs are manufactured by Insite ™ Process and Catalyst Technology and are available from The Dow Chemical Company as Affinity ™ Polyolefin Elastomers (POPs) and from DuPont Dow Elastomers, LLC as Engage ™ Polyolefin Elastomers (POEs). SLEP can be prepared in solution, liquid, or gas phase, preferably in the solution phase. The polymerization of ethylene and one or more non-essential alpha-10 olefin comonomers occur on geometrically restricted catalysts, as disclosed in European Patent Application 416,815-Α 〇 The term "substantially linear" means that, in addition to the short-chain branches of the homogeneous comonomer incorporated, ethylene polymers are also characterized by long-chain branches, so that the polymer main chain is replaced by a On average 0.01 to 3 long chain branches / 1000 carbons. Preferred 15 is a substantially linear polymer system used in the invention to substitute from 0.001 long chain branch / 1000 carbons to 1 long chain branch / 1000 carbons, and more preferably branch from 0.05 long chain / 1000 carbons to 1 long chain branch / 1000 carbons. "Long chain branch" (LCB) means a chain length of at least 6 carbons, more than this length cannot be discerned using a 13C nuclear magnetic resonance spectrometer. Each long chain branch has the same comonomer distribution as the polymer backbone and can grow up to the polymer backbone attached to it. The appearance of long chain branches can be determined by ethylene polymers using a 13c nuclear magnetic resonance (NMR) spectrometer and quantification using Randall (Rev · Macromol. 18 44 · 200406456 玖, description of the invention

Chem. Phys., C. 29, V. 2 & 3, p. 285-297). As a practical matter, current 13C NMR spectrometers cannot determine the length of a long chain branch exceeding 6 carbon atoms. However, other techniques known to determine the appearance of long chain branches in ethylene polymers include ethylene / 1-octene interpolymers. The second method is gel permeation chromatography with a low-angle laser light scattering detector (GPC-LALLS) and gel permeation chromatography with a differential viscosity meter detector (GPC-DV). Theories of using these techniques for long-chain branch detection and their dependencies have also been accumulated in the literature. See, for example, Zimm, G.H. and Stockmayer, W.H., J. Chem. Phys., 17, 1301 (1949) and Rudin, 10 A., Modern Methods of Polymer Characterization, John

Wiley & Sons, New York (1991) pp. 103-112, both of which are incorporated by reference. A. Willem deGroot and P. Steve Chum, both of The Dow Chemical Company, reported the material at a conference of the Federation of 15 Analytical Chemistry and Spectroscopy Society (FACSS) on October 4, 1994 in St. Louis, Missouri Demonstrating GPC-DV is a useful technique for quantifying long chain branches in SLEPs. In particular, deGroot and Chum found that the degree of long-chain branching in a homogeneous SLEP sample was measured to correspond well with the Zimm-Stockmayer equation to measure the degree of long-chain branching at 13C NMR. In addition, deGroot and Chum found that the presence of octene does not change the hydrodynamic volume of the polyethylene sample in water, that is, we can attribute the increase in molecular weight to the short-chain branching of octene to understand the percentage of moire in octene in the sample. From 19 200406456, the description of the invention removes the spiral of molecular weight increase caused by the short chain branch of 1-Xinfu, deGroot and Chum show that GPC-DV can be used to quantify the degree of long-chain branching of a substantially linear ethylene / Xinfu copolymer . deGroot and Chum also indicated that the logarithm of (12, melting index) is the logarithmic- (weight of GPC average 5 molecular weight) graph of the function. ) Is analogous to high-pressure, high-branched low-density polyethylene (LDPE), which is significantly different from ethylene polymers such as titanium compounds produced using Ziegler-type catalysts and general catalysts such as donor and starvation compounds used to make homogeneous polymers. 10 For ethylene / α-olefin interpolymers, the long-chain branches are longer than the short-chain branches formed by the incorporation of α-dilute hydrocarbons into the polymer backbone. The empirical effects that appear in the long linear branching of the substantially linear ethylene / α-olefin interpolymers of the α-olefins used have been augmented by enhanced hydrodynamic properties, which are quantitative and expressed as measured by Gas Extrusion Fluid (GER) The result and / or melt flow, 110/12, increases. 15 Contrary to the term "substantially linear", the term "linear" means that the polymer lacks measurable or showable long chain branches, that is, the polymer is substituted with an average of less than 0.01 long chain branches / 1000 Carbon. SLEPs are more obvious with: (a) — melt flow ratio, Ι (1) / Ι225 · 63, 20 (b) — molecular weight distribution, MW / Mn is determined by gel permeation chromatography and is defined by the equation: (Mw / Mn ) S (I10 / I2M.63, (c) A gas extrusion fluid mechanics makes the surface melt of SLEP 20 200406456 玖, the invention shows that the critical shear rate of crack initiation is at least 50% greater than that of a linear B起始 Initial critical shear rate of melt fracture of polymer surface ', where SLEP and the linear ethylene polymer contain the same comonomer, the linear ethylene polymer has a l2, Mw / Mn and a density of 5% Within ten and where the critical shear rate of each of SLEP and the linear ethylene polymer is measured at the same melting temperature using a gas extrusion fluid meter and a single differential scanning calorimeter, DSC, with a melting peak at -30 And 150C. 10 Critical shear rate and critical shear pressure versus melt fracture and other hydrodynamic properties such as fluid handling index (PI) are determined using a gas extrusion fluid gauge (GER). The Gas extrusion fluid measuring instrument By M. Shida, RN · and LV · Cancio in Polymer Engineering. Science, Vol. 17, No. 11, page 770 (1977), and in "15 Rheometers for Molten Plastics ^ by John Dealy, published by Van Nostrand Reinhold Co (1982) on page 97-99. The GER experiment was performed at a temperature of 190 ° C. A nitrogen pressure of between 250 and 5500 psig (1.7 to 38 MPa) was used with a diameter of 0.0754 mm and a length to diameter of 20: 1 ending at an entry angle. 180 ... For the substantially linear ethylene polymer described herein, 20 PI is the viscosity (in poise) of the surface of a substance as measured by GER at a surface shear pressure of 2.15 x 106 dyne / cm2 (0.215 MPa) for use in the invention. Of substantially linear ethylene polymers containing ethylene interpolymers and having a PI in the range of 0.001 poise to 50 poises (0.01 to 50 kg / cm.sec), preferably 15 poises (15 kg / cm.sec) or less Make the 20042004456, the description of the invention, the substantially linear ethylene polymer has a pi less than or equal to 70% of the PI of a linear ethyl polymer (— Ziegler polymerized polymer or a linear equal branch polymer (As described by Elston in US Patent 3,645,992) I2, Mw / Mn and density, each within ten percent based on 5-ene substantial linear ethylene polymer. The hydrodynamic properties of a substantially linear ethylene polymer can also be characterized by the Dow Rheology Index (DRI), which represents the "standardized relaxation time" of a polymer as a result of long chain branching. (See, S. Lai and GW. Knight ANTEC 993 Proceedings, INSITE ™ Technology Polyolefins 10 (SLEP) -New Rules in the Structure / Rheology Relationship of a -Oefin Copolymers, New Orleans, La., May (1993). DRI value Ranges from 0 pairs of polymers with no measurable long-chain branching (ie, Tafmer ™ products are available from Mitsui Petrochemical Industries and Exact ™ products are available from Exxon Chemical Company) to about 15 and are independent of the melt 15 index. Usually For low or medium pressure ethylene polymers (especially at low density), DRI provides an improved relationship to melt elasticity and high shear flowability, relative to the same relationship achieved in terms of melt flow ratio. It is substantially linear for the invention For ethylene polymers, DRI is preferably at least 0.1, and in particular at least 0.5, and most preferably at least 0.8. DRI can be calculated from the equation: 20 DRI = (3652879 * τ〇1 00649 / η〇-1) / 10 where τ is the characteristic relaxation time of the substance and η 〇 is the zero shear viscosity of the substance. Both τ〇 and ηο are "optimum" values for the Cross equation, as follows 22 200406456 发明, invention description η / η 〇 = 1 / (1+ (7 * τ〇) 1 * η) where η is the power law index of the substance, and η and 7 are the measured viscosity and shear rate respectively. The basis of the viscosity and shear rate data The line was determined to be obtained using a Rheometric Mechanical Spectrometer 5 (RMS-800) in dynamic scan mode from 0.1 to 100 radians per second at 160c and a Gas Extrusion Rheometer (GER) in extrusion waste from 1,000 psi to 5,000 psi (6.89 To 34.5 MPa), which corresponds to a shear pressure from 0.086 to 0.43 MPa, using a diameter of 0.0754 mm and a length-to-diameter 20: 1 mold at 19 0 C. Special material decisions can be made from 10 to 140 to 190 C It is necessary to accept the change of the melting index. A surface shear pressure versus surface shear rate diagram is used to indicate the melt fracture phenomenon and to quantify the critical shear rate and critical shear pressure of the polymer. According to Ramanurthy in the Journal of Rheology, 30 (2), 337-357, 1986. Above a considerable flow rate, the prominent irregularities 15 found can be roughly classified into two main types: surface melting fracture and overall melting fracture. Detailed and continuous surface conditions Loss of light from the surrounding sheet film gloss to the more severe "meal: fish forming surface ,,. Here, the “GER” described by “X” is characterized by the beginning of surface melt fracture (OSMF) 20, which is characterized by the beginning to lose outstanding gloss, and the rough surface of the protruding surface can be enlarged by 40 times. The substantially linear ethylene polymer melts on the surface: the critical shear rate for crack initiation is at least 50 percent greater than the substantially phase-independent phase of 5. w / Mm—the surface melting crack initiation of linear 2ene polymers 23 200406456 发明, Invention Description Critical Shear Rate. Bulk melting fractures occur under unstable, prominent flow conditions and range in detail from regular (eg, rough and smooth spirals) to irregular twists. For commercial acceptability to maximize film, coating and cast film performance 5 properties should also be minimized if surface damage occurs. The critical shear pressure at the onset of the melt fracture of the substantially linear ethylene polymer, especially those with a density greater than 0.910 g / cm3, used in this invention is greater than 4x 106 dynes / cm3 (0.4 MPa). Known substantially linear ethylene polymerization The material has excellent handleability, except that it has a relatively narrow molecular weight of 10 (ie, Mw / Mm & typically less than 2.5). In addition, unlike homogeneous or heterogeneously branched linear ethylene polymers, the melt flow ratio (I1G / I2) of a substantially linear ethylene polymer can be changed independently of the molecular weight distribution, Mw / Mn. Accordingly, the polymer main chain (A) of the polymorphic polymer composition of the present invention may be a substantially linear ethylene polymer. 15 Heteropolyethene, which can be used as the polymorphic long-chain branch (B) of this invention falls into two broad ranges, those prepared with a radical starter at high temperature and pressure, and those prepared with a Condition catalyst under high temperature and relative bottom pressure. The former is generally known as low density polyethylene (LDPE) and is characterized by branched chains of polymerized monomer units attached to the polymer's main chain. LDPE polymers usually have a density between 0.910 and 0.935 g / cm3. Ethylene polymers and copolymers prepared using a conditional catalyst, such as Ziegler or Phillips catalysts, are generally known as linear polymers because they substantially lack the branching of polymerized monomer units in the vicinity of the main chain. High density polyethylene (HDPE), usually has a density of about 0.941 24 200406456 玖, the invention description to about 0.965 g / cm2, is a typical monopolymer of ethylene or a copolymer of ethylene and a low degree of comonomer. And it contains relatively few branched linear copolymers relative to various ethylene and an alpha-olefin. HDPE is also well known, is available in a variety of grades, and can be used in this invention. Linear interpolymers of 5 ethylene and at least one alpha-olefin of 3 to 12 carbon atoms, preferably 4 to 8 carbon atoms, are also well known and highly commercially available. As is well known in the art, the density of a linear acetamidine / α-dilute hydrocarbon interpolymer is a function of the length of the α-olefin and the amount of the monomer relative to the amount of ethylene. The longer the length of the α-olefin The greater the amount of alpha-olefin olefin present, the lower the density of the copolymer. 10 The density of these linear polymers typically ranges from 0.87 to 0.91 g / cm3. Both substances are made from free-radical catalysts and auxiliary catalysts and are well known in this technology, such as their equipment methods. Heterogeneous linear ethylene polymers are available from The Dow Chemical Company as Dowlex ™ LLDPE and as Attane ™ ULDPE resin. Heterogeneous linear ethylene polymers can be prepared by the solution, fluid or gas phase polymerization of ethylene and one or more non-essential α-olefin comonomers in the presence of 15 Ziegler-Natta catalysts, as described in US · Patent No. 4,076,698 to Anderson et al. Heterogeneous linear ethylene polymers are typically characterized by a molecular weight distribution Mw / Mn, ranging from 3.5 to 4.1. A discussion of these two types of substances, and their preparation methods, can be found in U.S. Patent No. 4,950,541 and related patents. Heterogeneous polymers are differential scanning calorimeters (DSCs) with a linear main chain and a distinct melting peak due to high-density fractions greater than 115 ° C. Melting Code 25 200406456 发明, ethylene / α-olefins that are characteristic of the invention description line Interpolymer. Heterogeneous interpolymers will typically have a Mw / Mn greater than 3 (when the density of the interpolymer is less than 0.960 g / cm3), and will typically have a CDBI of less than or equal to 50, meaning that the interpolymer has different copolymerization monomers One of a mixture of molecules with different body contents and different amounts of short chain branches. 5 With reference to the properties of an ethylene polymer, which is well known as an ethylene polymer, various techniques have been developed to measure the crystallinity of ethylene polymers. When the ethylene polymer is absolutely derived from a hydrocarbon monomer (ie, when the ethylene polymer is a non-functional ethylene alpha-olefin interpolymer, the crystallinity can be determined from the density of the polymer to be used. The following equation: 10% C = (P-Pa) / P (Pc-Pa) x 100 where% < is the crystallinity percentage of the ethylene polymer, and Pa is the density of an ethylene polymer, which is 0% Crystallinity (ie, it is 100% amorphous, at room temperature (0,852g / cm3), Pc represents the density of an ethylene polymer at 100% crystallinity at room temperature (1,000g / cm3), and P is the density of a polymer whose percentage of crystallinity is determined to 15. The term "under negative and loaded service temperature" (ULST) is also referred to as "softening point under load" or "SPUL" and refers to the The temperature at which the needle was inserted into the polymer lnrni was reached to use a continuous force of 1N with a flat tip probe with a diameter of 1 mm when the polymer was heated from 25 ° C at a rate of 5 / min at a A device in the atmosphere of nitrogen 20. A device is a Thermo Mechanical Analyter (TMA) such as Model TMA-7 by Perkin-Elmer Instrume Supplied by nt Company. The method for operating this test is described in more detail in the following example section. 26 200406456 发明, invention description Higher density branched polymer (B) has a broad molecular weight range. On the low molecular weight side, the The branched polymer will have a Mn of at least 2000, preferably at least 3000. On the high molecular weight side, the branched polymer will have a 12 of at least 0.05 g / cm3. A typical melt index for the branched polymer ranges from 0.05 to 5 40 g / 10 min. 〇 When using a higher molecular weight branched polymer system, that is, a branched polymer with 12 less than 5g / 10m3, the number of branched polymer chains will require the presence of a high concentration of branched polymer, that is, The amount is greater than 20 weight percent (or a higher degree of free radical initiator is used, ie; the amount is greater than 10 weight percent to 0.5) to produce a given increase below the load use temperature. In contrast, when a lower molecular weight A branched polymer is used, and an increase in the short-chain branch (which is preferably a vinyl termination) will be selected to increase below the load use temperature, except that a relatively small amount of branch is used. Polymers, ie, amounts as small as 5 weight percent. 15 When not wishing to be bound by theory. It is generally believed that in the case of lower molecular weight branched polymers, low concentrations can be used, such as the polymorphic polymer composition Attached to more than one small branch attached to each polymer primary bond. As shown in Figure 1, it is generally believed that the presence of each main chain molecule will provide structural integration to the system regardless of higher usage Temperature is higher than 20 substances in the crystalline polymer backbone. Many methods for making the polymorphic composition of the invention can be found by those skilled in polymer science. In a specific embodiment, the higher crystallinity branched polymer and the lower 2004-20456 玖, invention description low crystallinity high aggregate polymer can be prepared to react the previously prepared and isolated polymer reactants. In this example, the more crystalline branched polymer will react to form a T-junction (to join) or a tandem (to light cross-link) with the lower-crystallinity backbone polymer. There are ways to complete this reaction to know who is familiar with the technique. In a specific embodiment, hydrogen will be extracted from the polymer backbone and will react with the branched polymer. Methods for extracting hydrogen from the polymer backbone include, but are not limited to, reactions that generate free radicals that decompose molecules uniformly (eg, compounds containing peroxides, or compounds containing azos, or radiation. 10 Unsaturation of olefins occurs On the main chain polymer or branched polymer can help control where the junction / cross-linking is located. For example, the peroxide breaks down in a large part of the main chain polymer and a small part of the ethylene terminated branch polymer The appearance of the polymer will be inclined to join the branched polymer to the main chain polymer, in which a vinyl-free branched polymer can reach hydrogen extraction to produce a radical which 15 will react with the main chain polymer to form Η -Linking. Vinyl-terminated branched polymer is prepared to adjust the reactor conditions so that the polymerization chain termination is eliminated with other hydrides, rather than hydrogen-terminated. In addition, adjuvants such as mono-, di- or triene-based functional molecules (such as : Triallyl cyanurate can be used to control the radical treatment more. Generally speaking, the bonding system is better to photo-bond, because more than 20 crystalline long chain branches can be incorporated) without The use of α-, Ω diene as a comonomer in the polymer formed in the higher branch or the polymer formed in the main chain will increase the reactivity of the polymer component. Suitable α-, Ω olefins Contains 1,7-octadiene and 1,9 decadiene 28 200406456 玖, description of the invention. When incorporated, the diene typically appears to crosslink or join with the polymer chain 0 in an amount less than 2. It can be performed in a solution of two polymers in an appropriate solvent or a melt mixing of the polymer ingredients. The latter is the preferred method 5. Melt mixing can be performed in a batch mixer such as a Brabender mixer, Banbury Mixer, roll honing, or in a continuous mixer such as a Farrell Continuous Mixer, or in a single or paired spiral extruder. Polymer formation is also possible, followed by irradiation or extraction of the reaction solution (such as peroxidation) And heating. However, melting and solution mixing are better in these methods than 10. In another embodiment, the composition of the invention can be prepared to copolymerize the branched polymer with the main chain polymer. monomer With a double catalyst system, it can be seen that the main chain polymer and the host composition (that is, the polymorphic polymer composition can be copolymerized at the same time. This method has reduced the high Tg / Tm polymer in a relatively cold reactor 15 Advantages of phase separation. In another embodiment, the composition of the invention can be manufactured in a series of dual reactor configurations, whereby the branched polymer is manufactured in the first reactor and then placed in a second reaction In the reactor, copolymerize with the monomers forming the main chain polymer to manufacture the main composition. The second reactor should be maintained at a temperature of 20 ° C, which is greater than the higher crystalline branch polymer will The temperature at which the lower crystallinity backbone polymer undergoes phase separation. The reactor in which the copolymerization reaction occurs in a reactor with a high polymer ("solid") concentration, such as a loop reactor, to maximize Polymerizable high crystallization in the reactor 29 200406456, " ^ * .., ... * ...-J-T-...., .. 玖, temperature of the branched polymer of the invention Department is better. In a specific embodiment, a single-site catalyst can be used to copolymerize higher crystallinity branched polymers of ethene and octane to make HDPE side chain branched ethylene / octene elastomers. Single-site catalysts, especially catalysts with a few restrictions, are better, where they have a higher molecular weight monomer and accept more traditional Ziegler catalysts or single-site catalysts without geometric restrictions. Unlike cross-linking, copolymerization avoids coagulation even at relatively high polymorphic long-chain branching content, as only one position is reactive at that long-chain branch. 0 10 preferably high Tm * T§ polymorphic long-chain branching The precursor monomer system is relatively low in diameter and has at least one diene terminal to spin each chain by means of copolymerization and dissolution of monomers in the processing solvent and / or diffused to the catalytic site. Not necessarily, a diene or polyolefin may be used as a comonomer of the one or two polymers to improve the incorporation / linking rate during the copolymerization reaction. 15 For example, an ethylene-diene or propylene-diene copolymer can be manufactured in one reactor. # A is placed in a first reactor in which it is copolymerized with ethylene or ethylene & propylene. If the degree of ethene is relatively low, coagulation can avoid increasing the rate of copolymerization reaction when the polymorphic branched precursor polymer and the polymer of the backbone polymer are increased. Chedi 'When a diene or propylene is used as a comonomer, it will constitute 20% by weight to less than 20% by weight, and more preferably less than 10% by weight of the composition of the invention. In another specific embodiment, the polymorphic polymer composition may be mixed with-or more similarly, additional polymers to the branched polymer or may be 200404456, the invention description and a high Tm or Tg formed therewith. The phases are crystallized via a solid phase solution or co-crystallisation. An example of the mixed component is high-density polyethylene. When the concentration of the branched polymer is low in the polymorphic polymer composition, the additional polymer is provided to cause the branch to copolymerize in one heat to obtain the desired physical properties and / or temperature resistance. Good. An excessively high crystallinity polymer will usefully co-crystallize with the higher crystalline branching of the polymorphic polymer composition to increase the thickness of the laminate, which will tend to increase the crystalline melting of the polymer composition temperature. In addition, this excessive amount of higher crystallinity polymer will be used to connect two separate higher crystallinity branches, which will increase the overall crystallinity of the polymorphic polymer composition, which will increase the crystallinity under load. Operating temperature. A preferred method of introducing the additional polymer is to add only an excess of branched polymer to the reactor or melt mixer so that when copolymerization or bonding or cross-linking occurs, the excess unreacted branched polymer remains unreacted. And co-crystallization or phase formation of this polymorphic long chain branch is available. 15 In another embodiment, the composition of the invention can be mixed with other polymers. For example, the composition of the invention can be mixed with other polyolefins, such as hetero-branched linear ethylene / α-olefin interpolymers, substantially linear ethylene / α-olefin interpolymers, ethylene / vinyl acetate copolymers, and styrene block copolymers. And amorphous polyolefins such as polypropylene and polybutene. 20 In a preferred embodiment, the polymorphic polymer composition will include at least one component that includes a polar molecular moiety. That is, the main chain polymer or the branched polymer is preferably functionalized to join a polar molecular moiety to itself. 31 200406456 发明, description of the invention Any unsaturated organic compound contains at least one position of the unsaturation of ethylene (for example, at least one double bond), at least one carboxyl group (-COOH), and it will contain up to one ethylene polymer It will be used for the purpose of this invention. As used herein, "carboxyl group" includes the carboxyl group itself and derivatives of the carboxyl group such as anhydrides, esters, and salts (both metallic and non-metallic). Preferably, the organic compound contains a position of an unsaturated bond of a carboxyl group of ethylene. Representative compounds include maleic acid, acrylic acid, methacrylic acid, decomposed aconitic acid, crotonic acid, alpha methyl crotonic acid, and lauric acid and their anhydride, ester, and salt derivatives, and trans-butene Diacids and their derivatives. The maleic anhydride dianhydride 10 is preferably an unsaturated organic compound containing at least one ethylenic unsaturated group and at least one carboxyl group. The unsaturated organic polymer system of the joined main chain polymer or branched polymer is preferably at least 0.01 wt%, and more preferably at least 0.05 wt%, based on the combination of the weight of the polymer and the organic compound. The maximum amount of unsaturated organic compound 15 can be changed as convenient, but typically does not exceed 10 wt%, preferably it exceeds 5 wt%, and more preferably it does not exceed 2 wt% of the joined polymer. Organic compounds can be joined to the desired or branched polymer by any known technique, such as those taught in USP 3,236,97 and USP 20 5,194,509. For example, in the '917 patent, the polymer was introduced into a two-screw mixer and mixed at a temperature of 60 ° C. The unsaturated organic compound is then added with a free radical starter, such as, for example, benzoic acid peroxide, and the ingredients are mixed at 30 ° C until the bonding is complete. In the 509 patent, the method is related

32 200406456 发明, description of the invention Except that the reaction temperature is higher, for example, 21 to 30. 〇, and a free radical initiator is not used or used at a reduced concentration. Another and preferred method of joining is taught in USP 4,95,541, using a devolatized broadcast of a pair of screws as a mixing device. The ethylene polymer and the unsaturated organic compound are mixed and reacted in the extrudate at a temperature at which the reactant melts and a radical starter appears. Preferably, the unsaturated organic compound is injected into a region maintained under pressure in the extrudate. A linear ethylene polymer is bonded with, for example, cis-butadiene anhydride, as shown in US 5,346,963. Incorporated here for reference. In the preparation of this polymorphic polymer composition, it was acknowledged that the presence of free radical initiators would lead to limited cross-linking of additional scaffolding polymers, directly to another or via dependent branches. If the degree of attachment is not sufficient to render the polymer composition unmanageable in a thermoplastic assembly or extrusion process, it is within the scope of this invention. Preferably, the polymorphic polymer composition will have less than 30 percent gel, more preferably less than 10 percent gel, and more preferably less than 5 percent gel. And optimally less than 2 percent gel. Optimally, the polymorphic polymer composition will be substantially gel-free. The polymorphic polymers of the invention do not necessarily contain antioxidants, fillers, extenders, UV stabilizers, lubricants and antiblocking agents, pigments, dyes, or blowing agents, based on those familiar with polymer formation Technician operation. When used, antioxidants typically appear in an amount of less than 0.5% by weight, preferably less than 0.2% by weight, based on the total weight of the composition. '' ν · '^-*; .. .... " ν r a 33 200406456 玖, description of the invention The composition of the invention can be usefully used for hot melt adhesion and pressure-sensitive adhesive composition. From this point of view, the composition of the present invention can be combined with an appropriate amount of more binder. Mix one or more waxes and / or one or more plasticizers. · 5 When used herein, this solution "binding agent" means that any of the many hydrocarbons is · The main composition is used to impart binding to the hot melt adhesive composition. For example, many types of binders include aliphatic A resins, polyterpene resins, hydrogenated resins, mixed aliphatic-aromatic resins, turpentyl esters, and hydrogenated turpentyl esters. · The binder used will typically have a viscosity of 350 ° F (177 ° C). When measured in terms of 10 Brook field viscosity, it is not greater than 300 centipoise (300g / cm.sec), preferably not more than 150 centipoise. (150 g / cm.sec), and preferably not more than 50 centipoise (50 g / crrrsec). The binder used typically has a glass transition temperature greater than 50 ° C. Basic aliphatic resins include those that are trademarked as Escorez 15 TM, Piccotac ™, Mercures ™, Wingtack ™, Hi-Rez ™, ·

Quintone ™, Tackirol ™ and more. Basic polyterpene resins include those available under the trademark Nivez ™, Riccolyte ™, Wingtack ™, Zonarez®, and others. Basic hydrogenated resins include those available under the trademark Escorez ™, Arkon ™, Clearom ™, and the like. Basic blended aliphatic-aromatic Group 20 resins include those that can be trademarked Escorez ™, Regalite ™,

Hercures ™, AR ™, Imprez ™, NorsoleneTMM, Marukarez ™, Arkon ™ M, Quintone ™ and more. Other binding agents can be used, and if they are compatible with the homogeneous linear or substantially linear ethylene, α-olefin interpolymer and non-certain 34 200406456, the wax of the invention description. The bonding agent typically appears in the hot melt adhesive of the present invention in an amount of less than 70% by weight, preferably less than 50% by weight. The bonding agent typically appears in the hot melt adhesive of the present invention in an amount of at least 55% by weight, preferably at least 10% by weight. The term "wax" is used to refer to a paraffin or crystalline ethylene simple polymer or interpolymer or material ethylene polymer, which has an average molecular weight of less than 6000. The basic polymer dissolved in this item contains an ethylene simple polymer available from Petrolite, #

Inc. (Tulsa, OK) with Polywax ™ 500, Polywax ™ 1500, and 10 PolywaxTM 2000; and paraffin are available from CP Hall under product designations 1230, 1236, 1240, 1245, 1246, 1255, 1260, and 1262.

PolywaxTM 2000 has a molecular weight of about 2000, a Mw / Mn of about 1.0, a density of about 0.97 g / cm3 at 16 ° C, and a melting point of about 126 ° C. CP Halll246 paraffin is available from CP Hall (Stow, OH). CP Hall 15 1246 paraffin has a melting point of 143 ° F (62 ° C), a viscosity at 210 ° F (99t) of 4.2 centipoise (4.2g / cm.sec), and a specific gravity at 73 ° F (23 ° C) was 0.915. The preferred waxes are prepared using a geometrically restricted self-catalyst. The polymer may be a simple substance of ethylene or an interpolymer of ethylene and a comonomer, such as C-C2 () α-olefin, styrene, alkyl-substituted Styrene, tetrafluoroethylene, vinylbenzenecyclobutene, non-conjugated diene, and naphthenic acid. The polymer, compared to traditional waxes, will have a "" 相对 11 from 1.5 to 2.5. Preferably from 1.8 to 2.2. The polymer was disclosed and * • '· ... ..... .. 35 200406456 玖, the invention description application was filed in US Potent Application Serial No. 784,683 on January 22, 1997 ( WO 97/01181). The wax has an average molecular weight of less than 6000, preferably less than 5000. The wax will typically have an average molecular weight of at least 800, and preferably at least 5 1300. The wax having the hot-melt adhesive used in the invention, when it is an ethylene simple polymer (a traditional ethylene simple polymer wax or an ethylene simple polymer prepared from a geometrically restricted catalyst) or ethylene and a An interpolymer selected from a group of 10 monomers consisting of C3-C2G α-olefin, non-conjugated diene, and naphthenic acid will have a density of at least 0.910 g / cm3. The second polymer has a density of not more than 0.970 g / cm3, preferably not more than 0.965 g / cm3. The polymorphic polymer composition of the present invention is usefully used for pressure-sensitive adhesive composition, and the branched polymer at its higher crystallinity is to improve the sealing time of the adhesive. As the adhesive cools, the branched polymer crystallizes 15 while the polymer backbone remains soft and / or self-flowing. This gives the adhesive strength during the setting process and reduces the opening / sealing time. The hot-melt adhesive (especially the pressure-sensitive adhesive may further include an oil or other plasticizer, such as an amorphous polyalkylene hydrocarbon. The oil is typically used to reduce the viscosity of the hot-melt adhesive. When used Oil will appear in an amount of less than 20 percent, preferably less than 15 percent, and most preferably less than 10 percent by weight, based on the weight of the hot melt adhesive. Basic types of oil Contains white mineral oils such as Kaydol ™ (available from Witco), and Shellflex ™ 371 naphthenic oil (available from Shell Oil Company). Oil reduces the viscosity of the hot melt adhesive 36 200406456 They should not be used to the extent that they are detrimental to the intended use. The hot-melt adhesives of this invention can be prepared by standard melt-blending methods. In particular, polymorphic polymer compositions, optional binders, The optional 5 wax, and optional plasticizer, can be melt mixed and heated (from 15 to 20 (rc) under an inert gas environment to obtain a homogeneous mixture. Make a homogeneous mixture without destroying the heat Any method of mixing the melt components is possible, Through the use of a heating device and a stirrer, in addition, the polymorphic polymer composition, any soil, any binder, and any plasticizer can provide the application of the substrate to one. The applicator is broadcast. A suitable corresponding inductive adhesive will show a probe binding of at least 200 grams, more preferably at least 300 grams, and most preferably at least 300 grams. A suitable pressure sensitive adhesive will be more Shows a heat resistance which is at least 1 (rc, preferably at least irc, and more preferably at least 20 ° C greater than 15 systems in which the branched polymer and main chain polymer are used as a mixture instead of the polycrystal of the invention The type of polymer composition is for pressure-sensitive adhesives. Suitable adhesives will have a viscosity low enough to allow smart use in the desired texture. Typically, hot-melt adhesives will melt. Viscosity at 350 ° F (177 ° C) is typically preferred because viscosity is lower than 20 due to 50,000 centipoise (50,000g / cm · sec). Use of the polymorphic polymer composition of the present invention ( Especially those in which at least one main chain polymer or branched polymer is The polar molecular part is used as a functional group) will further include, but not limited to, gaskets such as those in automotive windows,

37 200406456 发明, Description of the invention Sealed 'Adhesive, Insulation and Encapsulation of Elastic Molded Articles such as Shoe Sole, Wires and Cables' Roofing Film, Floor Coverings, Rubber Water Pipes, Boots, Car Parts' and Other The industry needs a portion of an elastic substance that adheres to an elastic substrate. 5 [Implementation of the cold type] The following examples, which present a representative polymorphic polymer composition of the invention, are proposed for demonstration purposes, and are not limited thereto. m. An example of a polymer made from the bristles Polymer A1- A substantially linear ethylene 10-octene copolymer prepared according to the teachings of US 5,278,236, which has a measured 12 0.94 g / 10min and a density of 0.869 g / cm3 . Polymer A2-—A substantially linear ethylene octene copolymer prepared according to the teachings of US · 5,278,236, which has a measured I2 of 3.86 g / iomin and a density of 0.867 g / cm3 〇15 Polymer A3—according to US · 5,278,236 teaches a substantially linear ethylene octene copolymer prepared with a measured I2 of 23.79 g / 10min and a density of 0.867 g / cm3. Polymer A4-a substantially linear ethylene / octane copolymer prepared according to the teachings of US 5,278,236 The object 'It has a I2 30 g / 10min, and a density of 0 gw / cm3 20 〇 Polymer A5-- a substantially linear ethylene / octane copolymer prepared according to the teaching of US 5,278,236' It has a density of 0.870 g / cm3 and —Igg / iomin. Polymer A5—A substantially linear ethylene prepared according to U.S. 5,278,236 teaching 38 200406456 玖, description of the invention ene / octene copolymer, which has a density of 0.870g / cm3 and an I2 18g / 10min. Polymer A6—A substantially linear ethylene / octene copolymer prepared according to the teachings of US 5,278,236, which has a measured I2 lg / 10min and a density of 0.855 g / cm3. A5—A polymer prepared according to the teachings of US 5,278,236 A substantially linear ethylene / 1-octane copolymer having a density of 0.855 g / cm3 and a refining index of 30 g / 10 min. Polymer A8—10—very low molecular weight ethylene / 1-octene copolymer prepared according to the teachings of US Patent Application Serial No. 784,683, filed Jamary 22, 1997 (WO 97/01181), with a density of 0.855 g / cm3 and A melt viscosity of 350 centipoise (350 g / cm · sec) at 350 ° F (177 ° C). Polymer A9—A substantially linear ethylene / 1-octene copolymer prepared according to the teachings of US 5,278,236, which has a density of 0.855 g / cm3 and a melt index of 0.5 g / 10 min. 0.15 Polymer A10—is according to US 5,278,236 Teaching to prepare a substantially linear ethylene / 1-octene, which has a density of 0.870 g / cm3 and a melting index of 30 g / 10 min. Polymer Bl—HDPE 55500—an ethylene / butene copolymer provided by Phillips Petroleum, which There are measured I2 49g / 100min and density 20 0.955g / cm3. Polymer B2--Marlex-50-100 high density polyethylene has a density of 0.952 g / cm3 and a density of 0.08 g / 10 min, and is available from Phillips. • Blend B3—Dowlex ™ 25355 high density polyethylene has a density of 39 200406456 玖, invention description 0.955g / cm3 and an I2 25g / 10min. Polymer B4—Dowlex ™ 25455 high density polyethylene has a density of 0.955g / cm3 and an I2 of 25g / 10min. Polymer B5—A substantially linear 5 ethylene / 1-octene copolymer prepared according to the teachings of US 5,278,236, which has a density of 0.902 g / cm3 and a melting index of 30 g / 10 min. Polymer B6—prepared according to the teachings of US 5,278,236 A substantially linear ethylene / 1-octene copolymer having a density of 0.913g / cm3 and a melting index of 30g / 10min. 〇10 Polymer B7--Attane ™ 6152 very low density polyethylene, a heterogeneous linear ethylene / 1-octene Ethylene copolymer has a density of 0.904 g / cm3 and a melt index of 0.5 g / 10 min. Polymer B8—15 extremely low molecular weight ethyl ester prepared according to the teachings of US Patent Application Serial No. 784,683, filed January 22, 1997 (WO 87/01181). The F / 1 copolymer has a density of 0.9 55 g / cm3 and a viscosity of 350 centipoise (5000 g / cm · sec) at 350 ° F (177 ° C). Polymer B9—Dow HDPE 12165 has a density of 0.955@/〇113 and a melt index of 1.08 / (: 1] 13. Polymer B10—Dow HDPE 25355 has a density of 20 〇.955 & / 〇113 and a dissolution index 1 (^ / 1〇11 ^ 11. Polymer C: a polymer mixture prepared in a reactor prepared by the low WO 94/17112 method, which has its target composition: 68.5 A wt% of a substantially linear ethylene / octene copolymer has a density of 0.861 g / cm3 and an I2 of 0.29 g / 10min and 40 200406456 玖, invention description 3 1.5 wt% of a high-density polyethylene having a density of 0.946 g / cm3 and I2 370g / 10 min 〇 Polymer D—— maleic anhydride-linked high-density polyethylene has a density of 0.953g / cm3, a melting index of 9g / 10min, and a weight percentage of 1.2 · 5 Butadiene anhydride is prepared from reactive extrusion of high density polyethylene and maleic anhydride with a density of 0.953 g / cm3.

Lupersol 500R (99 ° / 〇 pure di-cumulative alkenyl peroxide, available from Elf Atochem) ° Lupersol-130 (90-95% of 2,5-dimethyl-2,5-bis (t-butyl peroxide) (Oxy) hexyne-3, available from Elf Atochem). Lupersol-101 2,5-di 10 methyl-2,5-di (t-butylperoxy) hexane (available from EH Atochem). Test Method for Evaluating the Composition of Examples and Comparative Examples The temperature under load (ULST) is measured using a thermomechanical analyzer (TMA). The penetration is measured with respect to temperature. The temperature at which the probe penetrates imm is used as the operating temperature under load. A heating rate / min and a load of 102 g 15 were used. A Rheometrics Solid Analyzer Model RSAII was used to determine the rate of change with respect to temperature. The sample was compression-molded to a sheet of approximately 0.25 mm thick to be maintained at 1500 psi (10.3 Mpa) and 350 ° F (177 ° C) for 5 minutes, and then cooled to 27 °? / 11 ^ 11 (-2.8. 1 丨 11) to 90 卞 (32. (:). The sample is maintained at 90 2F (32 C) for 1 minute and the receiver is removed from the compression. A condition of 10 rad / sec frequency is tested in the twisted rectangle and starts At -145 ° C and increase to 120 ° C or 150 ° C or 270 ° C at a step size of 5 ° C with an infiltration time of 30 seconds for each step, under nitrogen atmosphere. • ^-·... . · · »---... 41 200406456 玖, description of the invention The gel composition was determined to be extracted by xylene according to ASTM 2785, Method A. The pressure and tension are at 23 ° C and 70 ° C. The measurement is in accordance with ASTM D-1708. The values in parentheses are the pressure and tension at 70 ° C. The hardness of pillar A is measured in accordance with ASTM D2240. '5 The ultimate tension measurement is in accordance with ASTM-1708 using a micro-tension bar. Decided to use a Brookfield Laboratories DV Π + Viscometer in a disposable aluminum sample tank according to the following method. The shaft used was a SC-31 hot melt shaft, suitable for measuring viscosity in the range from 10 to 100,00 0 centipoise (10 to 100,0008 / 〇11 * 36 (:). All slice knives are used to cut 10 samples into small enough pieces to fit the 1 inch pair (2.5cm) width, 5 inch pairs (12.5 cm) ) Long sample cell. The sample is placed in the cell, which is then inserted into a Brookfield Thermosel and locked into place with a bent back and forth probe. The sample cell has a notch in the base that conforms to the bottom of the Brookfield Thermosel to ensure that the cell cannot The rotation is when the shaft is inserted and rotated. The sample is heated to 350 ° F (177 ° C) 15 while another sample is added to the molten sample approximately 1 inch (2.5cm) below the top of the sample cell φ The viscometer device is lower and the shaft sinks into the sample slot. The reduction is continued until the small basket of the viscometer and Thermosel are in line. The viscometer is opened and segmented to all breakage rates so that a torque reading is in the range Percents 30 to 60. Read out and take it out every minute to 15 minutes, or when the value is stable, the final value of 20 is recorded. Example 1-3: Determine the reaction of the polycrystalline pad polymer composition of the invention Amount of branched polymer-a Haake Rheocord System 40 torque flow meter with a Rheomix 42 200 406456 玖, description of the invention 600 mixer and roller type mixing blades were used to prepare the composition of these examples. The mixture was prepared by mixing the ingredients at 75 rpm at 145 ° C. The composition of the polymers A2, A3, and B was provided thereon. Lupersol 500 (99% pure cumulative dilute peroxide, available from Elf Atochem) is added at a specified amount of 5 and the resulting mixture is mixed for about 1 minute at 145 ° C, the temperature rises to 175 ° C, and The samples were mixed for a total of 15 minutes. The samples were placed on a cooled compression mold platform while still hot and compressed into a sheet for FTIR analysis of vinyl content. The FTIR analysis of the representative composition of this invention is set in Table 1. Table 1 Vinyl analysis of Examples 1-3. Example 10 describes Vinyls / 1000C before peroxide. Vinyl / 1100OC after peroxide. Vinyl 0 / 〇1 40.2g 50/50 polymer A3 and polymerization. Compound B1 + 0.20g Lupersol 500R 0.448 0.167 63 2 40.2g 50/50 polymer A2 and polymer B1 + 0.20g Lupersol 500R 0.735 0.206 72 3 40.2g 50/50 polymer A3 and polymer B1 Mixing + 0.50g Lupersol 500R 0.636 0.069 89 The reduction of the shrinkage in the final group of Acetylate can be seen as the degree of the formation of the "T" link 43 200406456. Because the hydrogen that can be extracted from polymers A2 and A3 can be set to have approximately the same probability as the hydrogen that can be extracted from polymer B1, most of the vinyl families are higher in this lower molecular weight polymer B1 than in this Molecular weight polymers A2 and A3 (a mixture of 50:50 polymer components is used), which can be set to about 50%. The "T" connection is attributed to the joining of polymer B1 to polymers A2 and A3 . The strong reduction in vinyl concentration is shown in Table 1 to further demonstrate the formation of `` T '' linkages. The high crystallinity polymer B1 supports the branching of the main chain with great changes in temperature resistance as described below EXAMPLES Examples and Comparative Examples 4-18: An improved Haake Rheocord System 40 torsional rheometer exhibited by the polymorphic polymer of the present invention at a temperature resistance of 10—a Rheomix 3000E mixer and a roller-type mixing blade were used. The sample is equipped to melt the mixed polymer B1 and the usable polymer A1, A2, and A3 resin together at 60 to 70 revolutions per minute and about 145 ° C for about 4 minutes. Lupersol 500R (15 99% pure dicumene) Base peroxide, available from Elf Atochem) was added as indicated. The mixer speed was increased to about 160 rpm and minutes to quickly mix with the peroxide to create a viscous heating effect, which was within 1-2 minutes Process, raising the temperature of the mixture to about 190 ° C, causing decomposition of the peroxide. The mixer speed was reduced to 60 rpm to one minute. After mixing, the mixer 20 was stopped and the sample was removed and the Cool. The polymer block Then make it into a granule 44 200406456 & thin a tartar uil > l .13 rir > 1720/1177 (11.86 / 8.115) 2839/1966 (19.57 / 13.56) 2904/2585 (20.02 / 17.82) 2614/3020 ( 18.02 / 20.82) 1628/1635 (11.23 / 11.27) 1875/2307 (12.93 / 15.91) 2335/2845 (16.10 / 19.62) 2662/3036 (18.35 / 20.93) 1164/1238 (8.025 / 8.536) 910/1099 (6.28 / 7.577) 953/1312 (6.57 / 9.046) 936/1680 (6.453 / 11.58) 1790/2700 (12.34 / 18.62) 2306/2923 (15.90 / 20.15) 2253/3367 (15.53 / 23.22) Percent extension without peroxide / yes Peroxide 946/972 892/427 790/423 812/437 1317/1048 1218/756 1089/621 50/482 1341/1285 1496/1253 1385/961 790/895 715/865 761/656 17/67 Maximum temperature * (. 〇-peroxide-free / peroxide 65/65 125/135 90 ^ 150 130 ^ 150 55/65 110 ^ 120 80/110 95/127 50/55 105/115 85/115 70/130 75/127 115/128 130M20 1 mile ^ 2 ^ ^ See "¥ ^ 4 cockroach 6 carbon temporarily 6.33 / 0 16.24 / 0 44.52 / 0 118.06 / 0 33.08 / 0.58 61.44 / 0.23 113.13 / 0 196.61 / 0 145.44 / 11.1 140.68 /9.07 167.84 / 3.39 203.17 / 1.33 232.37 / 0.28 276.52 / 0.1 350.25 / 0.04 Sample density (g / cm3)-without peroxide / with Compound 0.8714 / 0.8716 0.8931 / 0.8887 0.9132 / 0.9060 0.9329 / 0.9239 0.8697 / 0.8698 0.8898 / 0.8882 0.9109 / 0.9058 0.9328 / 0.9240 0.8683 / 0.8687 0.8739 / 0.8738 0.8818 / 0.8812 0.8890 / 0.8877 0.9103 / 0.9066 0.9317 / 0.9249 0.9547 / 0.9410 Polymer B1. tn < N in 〇CN jn 〇 (Ν in ο τ-Η polymer A3 〇 〇 〇〇〇〇〇〇〇〇 〇 00 00 OO 〇 polymer A2 〇 〇 〇〇〇r-Η in (N 〇 ο ο 〇 〇ο Ο Polymer A1 〇r— < κη (ΝΟΟ 〇〇〇〇〇〇 ο ο ο ο ο Comparative Example 4a / Comparative Example 4b Comparative Example 5 / Example 5 Comparative Example 6 / Example 6 Comparative Example 7 / Example 7 Comparative Example 8a / Comparative Example 8b Comparative Example 9 / Example 9 Comparative Example 10 / Example 10 Comparative Example 11 / Example 11 Comparative Example 12a / Comparative Example 12b Comparative Example 13 / Example 13 Comparative Example 14 / Example 14 Comparative Example 15 / Example 15 Comparative Example 16 / Example 16 Comparative Example 17 / Example 17 Comparative Example 18a / Comparative Example 18b 200406456 玖, Description of Invention Table 2 shows the blend of Comparative Example 15, that is, the blend that is not treated with peroxide, and fails at 70 ° C. Due to the melting of polymer A3 crystals, the mix was provided with sufficient strength to maintain its integrity in the RSA test and this sample sample was destroyed. In contrast, the multi-type polymer composition of Example 15, i.e., 5 has a peroxide-treated composition, and maintains integrity to 130 ° C, which is about the melting point of polymer B1. Table 2 summarizes the results for a series of this comparative mixed composition (prepared without peroxide treatment) and a series of polymorphic polymer compositions of the invention (prepared treated with peroxide). Table 2 shows that the polymorphic composition of the present invention has significantly improved temperature resistance than the comparative blend. In addition, Table 2 shows that the pure polymers A1, A2, and A3, which are treated with peroxides, additionally fail at relatively low temperatures. Therefore, the substantial improvement in the temperature resistance of the polymorphic polymer composition of the present invention cannot be attributed to the formation of a cross-linked network, but should be attributed to the addition of the high-melting polymer B1 branch to the formation To polymerize the main chains of Al, A2, and A3. Examples 19-23: Effects of peroxides on the physical properties of polymorphic polymer compositions Comparative Examples and Preparation of Polymorphic Polymer Compositions of Examples 19-23 Following the method previously set forth in Examples 1-4. The composition of the polymorphic polymer composition and the comparative mixture, and the properties obtained are set forth in Table 3 below. 46 200406456 lw Example 25 〇100 in o 120 ND ND OO Comparative Example 24 〇100 o ND ND OO Example 23 S od S 1800/260/200 (12.4 / 1.79 / 1.38) 1000/330/215 Examples… 〇o 0.5 130 1900/700/470 (13.1 / 4.83 / 3.24) 290/120/120 5: Example 21 (N o in O 120 4300/560/250 (29.6 / 3.86 / 1.72) 480/150/130 S Examples 20 CN omd 100 1800/220/180 (12.4 / 1.52 / 1.24) 1200/360/330 VO OO | Comparative example (N o O 0.5 730/60 (5.03 / 0.41) 1400/20 00 Example composition polymer A3 (wt %) Polymer B2 (wt%) Polymer (wt%) Lupersol 500R (wt%) Properties ULST (° C) Gel (%) Pressure (psi (MPa)) Tension (%) 23/70/100 ° C si λ < < 〇m iS ® 1¾ 200406456 玖, the description of the invention i9-2m reading. Compared to Example 19-21, when the amount of peroxide increases, the use under load / jnL degree also increases the mouth, Take 27 C in the example of Example 20 and 47 ° c in the example of Example 21. The results shown in Table 3 show that the polymorphic polymer composition of the invention of Examples 20 and 21 has a #parent comparative consistency Comparative Comparative Mixing of Example 19 Far higher heat resistance. This is shown in Figure 3. This shows that the polymorphic polymer compositions of Examples 20 and 21 endure a temperature before the hardness of the support a decreases to 45 compared to the comparative example to 19. This See more in Figure 4, which shows that the polymorphic polymer compositions of Examples 20 and 21 were penetrated to a higher temperature by a probe of 1 mm than Comparative Example 19. Table 3 further indicates the polymorphic polymer composition The material has tensile properties that exceed the comparative mixture of Comparative Example 19 at elevated temperatures. For example, the blend of Comparative Example 19 loses most of its tension at 70 ° C. In contrast, the polymorphic polymer compositions of Examples 20 and 21 Each exhibited a tension of 25 ° (1.72 MPa) and 180 psi (124 MPa) at 100 ° C. In addition, the polycrystalline polymer composition of Examples 20 and 21 had less gel content than the previous work. Part of the chain is mixed, for example, US 3,806,558, which reveals a gel content greater than 30 percent. Surprisingly, the polymorphic polymer composition exhibited such a large improvement in properties at high temperatures without greatly reducing elasticity and softness, and without the formation of a significant amount of a crosslinked network structure. f. Discussion of Examples 21-23. Compared to Examples 21-23, the use temperature under load increases as the concentration of the polymer formed by the high crystallinity branch increases. It is interesting to note that when between Examples 23 and 21, an increase in the amount of high crystallinity material from a weight percentage of 20 to 25 makes an increase in the use temperature of 40 ° C under load. Discussion of Examples 24-25. Examples 24 and 25 demonstrate high crystallinity polymers and low crystallinity polymers ^ 7 Λ 48 200406456 玖, description of the invention The mixture of the compound produced in the reactor can be advantageously made into the polymorphic composition of the invention. It should be noted that the polymorphic polymer composition of Example 25 exhibits a use temperature under a load which is higher than that of the non-reacted mixture in the reactor of Comparative Example 24 at 40 ° C. Examples and Comparative Examples 19-20 and 24-25 Transmission electron micrographs (ΊΈM) of polymorphic polymer compositions. The polymorphic polymer compositions and comparative mixtures were compression molded into space. It is a 1-inch (2.5cm) inner diameter and% -inch (0.16cm) thick dish at a mold temperature of 177 ° C, and then cooled to 22 ° C at a rate of 15 ° C / min. before. The thin long piece of the compression mold sample was embedded in Epofix (Struers epoxy-based embedding kit) at room temperature. After modifying this small piece 'these were dyed in trichloride and bleach for two hours at room temperature. Ultrathin sections with a thickness of about 1000 angstroms were collected at room temperature using a Reichert-Jung Ultracut to obtain a set of sections. The sections were placed on a fermwa-coated copper grid. The sections were viewed using a JEOL 2000FX TEM at a 100 kV force σ speed voltage and a magnification of 30,000 times. Digital analysis of TEM images was performed on a LeiCaQuantimet 570 grayscale analyzer. The grayscale image is input to each image through a CCD image to enlarge and increase and set the zero point. The creation of binary images containing disperse phases and their respective layers is delimited in grayscale. These binary forms are opened with large and small horizontal and vertical manipulators to remove the respective laminations from the matrix. The background noise is opened in a pattern and the size of the small disc is removed. Manual operations then proceed to correct residual errors. For a description of the image transformations used, see "Image Anajysis — Mathematieal 'Vol.l, by Jean Serra ^ Academic Press (1982). Digital image analyzers measure 8 parts of the disperse phase and the total area from the bipartite in each disperse phase. I ...- · ..- ~ ...... 49 200406456 玖, the diameter of the invention. The statistical diameter is calculated from the average diameter of each dispersed phase. These statistics are straight and the size of the phase and Information on the size of the size distribution. The volumetric mean diameter emphasizes the appearance of large features, while the blended mean diameter emphasizes the small features. The TMM image of Comparative Example 19 is shown in Figure 5, magnified at 30,000 times. Micrograph It shows a two-phase morphology containing dispersed higher density polyethylene fractions in a continuous matrix of the elastomeric phase attributable to the polymer. The portions of the higher density polyethylene composition attributable to the polymer B2 are distinguished by their lamination The patterns are all present and diverging into and out of the matrix. The elastomer phase of the lower density polyethylene component due to polymer A3 shows the characteristic grainy grained microparticle crystals. In contrast, Example 20 The TEM image of the crystalline polymer composition is shown in Figure 6, magnified at 30,000 times. When the micrograph shows a two-phase pattern, it can be attributed to the dispersed higher density polyethylene phase of polymer B2. The average field size is significantly lower than that in Figure 5. The good dispersion system laminated in the elastomer phase is consistent with the belief that the higher density polyethylene component of its polymer B2 is joined to form an elastomer with polymer 8.3. The main chain. The TMM images of Comparative Example 24 and Example 25, magnified at 30,000 times, are located in Figures 7 and 8. The volume portion of the dispersed high-density polyethylene phase was determined to be analyzed by digital images. The volume and size of the high-density polyethylene dispersed phase of the polymorphic polymer composition are set out in Table 4 below. 〇50 200406456 玖, Description of the invention Μ 口 口 着 / 〇 Office floor average diameter is realistic 192 025 052 156 Ezina 245 0.13 036 1.43 Practice 8.1 0.19 026 153 Practice 8.0 0.18 020 034 As set in Table 5, the polymorphic polymer composition of Example 20 of the invention shows a higher than 50% less Island of crystallinity (if proven A significantly lower volume percentage was compared to the unreacted mixture of Example 19. Similarly, the polymorphic polymer composition of Example 25 of the invention did not exhibit 67% less of the higher crystallinity island region ( As demonstrated by a significantly lower volume percentage) than the unreacted mixture of Comparative Example 24. This means that the polymorphic composition of the invention actually contains an elastomer backbone which is joined by the higher density polymer component. An average of the volume percentages of Car Parents 19 and 24 is 22%. One of the volume percentages of Examples 20 and 25 is an average of 8. On this basis, it is estimated that 64% of the total high-density polyethylene elastomer pipe rack. Polymorphic Ethylene Polymer of Pressure Sensitive Adhesive The next polymer was used to prepare the polymorphic polymer composition of this example. The samples were prepared by dissolving the mixed polymers A6 and D in the indicated amounts in a H ^ ake Rheocord System 40 Torque Flow Torque with a Rhe ^ 300E cylindrical mixing blade at 60 to 75 revolutions per minute and about 145 ° C. About 4 minutes. Lupersol ™ 101 (available from Elf Atochem) is added to refer to the amount of 51 200406456 说明, the description of the invention, and the mixer speed is increased to about 160 revolutions per minute to quickly mix it and cause a viscosity heating effect, and in This process takes 1-2 minutes and raises the temperature to about 190 ° C to decompose the peroxide. Mixer speed drops to 60 rpm for another minute. After mixing, the mixer is stopped and the sample is removed and allowed to cool. The polymer mass is then granulated. The resulting polymorphic polymer and a comparative polymer were mixed to test their effectiveness as a pressure-sensitive adhesive for tapes. The following adhesive composition was used: 100 phr resin, 220 phr

Escorez 1310LC binder, and 1 phrlrganox ™ 1010. The composition is stunningly mixed in no C in a Haake. From reaching a substance mix, 80 phrkaydol oil was added via a syringe. Tape The sample was prepared by compression molding an adhesive formed between a Mylar ™ membrane and a release plate at 170 ° C under a pressure of 20,000 psi (138 MPa). The thickness of the adhesive is about 2mil (0.05mm). The heat resistance of the resulting adhesive was measured using a mechanical mechanical spectrometer. The temperature of the storage rate (G,) on the rubber platform suddenly decreases as the heat resistance temperature. A temperature scan run is delayed from about -70 ° C to 200 ° C at a balance of 5t / step for 30 seconds per step. Vibration is 1 degree / second, and the auto-tension function is used to start the tensile force of 0.1%, increase by 100 to 100 when the torque is reduced to 4 grams-cm. The maximum pulling force is set to 100%. The 76-ga tablet device was started with a “HOLD” function and the device was cooled to the thief and the test was started. It corrected for thermal expansion or contraction to measure _ mouth heat or cooling. A nitrogen environment was maintained In the whole process of the experiment to reduce the damage caused by oxidative factors. Probe combination measurement Xana 7 uses a retention time of 10 seconds and-probe separation rate lCM / sec 〇 52 200406456 发明, description of the invention

Viscosity was measured at 177 C series. A Brookfield Labomtories DV + Viscometer was used in a disposable aluminum sample chamber according to the following method. The shaft system used is sc_3i hot melt shaft. The sample was cut into small enough pieces to fit into the 1-inch (2 · 5αη) wide and 5-inch (12.5 cm) long sample cavity. The sample was heated to 177 C to dissolve the sample approximately 1 inch (2.5 cm) below the top of the sample cavity. The viscosity device is lowered and the shaft is immersed in the sample cavity. The viscometer was turned on and set to all fractions which led to a torque reading in the range of 30 to 60 percent. The reading is taken out for a total of 15 minutes per minute, or until the value is stable, its final value is recorded. Polymorphic polymer compositions and comparative polymers, their properties, and functions such as pressure-sensitive adhesive composition are set in Tables 5 to 7. What? Oral gatherings, butterflies, gatherings, gatherings, ^ D. Appearing, moving, and weaving, Kph), Teng Nen, and more, aS! Julianxian * i * r), multiple turnings, ^ DLST CO, reading fiber 丨 Thief 1 emblem (For thief) 黍 emblem thief at nrcmmm (jgfcm · sec)) 21-1 ----- — 78 22 05 115 380 110 46,000 (46 ^ 000) 21-2 78 22 0 58 630 80 ^, 000 ( 42,000) 踯 ------ Conduct 370 lose m

The results in Table 5 show that polymorphic polymers can be used as a pressure-sensitive adhesive: the sample has an acceptable processability, probe binding (compared to commercially available Scottish Magic Tape), and a more comparable mixture High use temperature. 53 200406456 Guilt, description of invention Table 6 Composition of polymorphic polymer composition 26-39 m Di Laigang and Lupersol 101 (phr) 26 A6 m 78.0 2Z0 05 27 A6 m 70.0 30.0 05 Moth decoration 7 A6 B4 70.0 30.0 0 28 A6 B5 70.0 426 0.7 tfc | Feeder ¢ 8 A6 B5 m 416 0 29 A6 B5 40.0 60.0 05 30 A6 B6 70.0 30.0 05 31 A6 B7 70.0 30.0 05 32 A6 D 70.0 30.0 05 33 A6 B5 70.0 30.0 05 34 A7 B3 78.0 m 1.0 35 A8 B3 78.0 m 1.0 36 A7 B8 7 & 0 220 1.0 37 A7 B9 7 & 0 2Z0 1.0 38 A7 BIO 7 & 0 2Z0 1.0 39 Α »Ά8 B3 50ptrA9 28phrA8 220 1.0 Table 7 Pressure sensitive Adhesive to destroy the multi-winged wing to aggregate the life J / tt # Miscellaneous multi-day miscellaneous regulations E131〇J〇0r) Ka ^ dd m IMACO G, just (φΠ £ 8 ^ ΐPrice Robe Tack (g) Tg (° 0 21 -1 26 100.0 220.0 80.0 115 3x l (f 430 -3 21-2 27 100.0 230.0 80.0 122 2x l (f 380 1 21-3 Nendu ¢ 7 100.0 220.0 80.0 58 3x \ & 510 0 214 28 100.0 230.0 80.0 m 3x l (f 380 -9 21-5 100.0 220.0 80.0 63 7k ltf 400 2 21-6 29 mo 220.0 80.0% 2x l & 200 0 21-7 30 100.0 220.0 80.0 95 lx \ (f 300 0 21-8 31 100D 220.0 80.0 92 6κ 105 380 0 21-9 32 100.0 220.0 80.0 120 3x l (f 320 0 21-10 33 110.0 110D 40.0 84 ND ND ND 22-1 34 100.0 220.0 80.0 117 3x l (f ND 0 22-2 35 100.0 230.0 80.0 75 4 < 105 ND 0 22-3 36 100.0 220.0 SOD m 3x 10? ND 3 224 37 100.0 220.0 80.0 108 6 < \ (f ND 0 22-5 38 100.0 230.0 80.0 109 9x 10? ND 4 m 39 MO 220.0 m 95 ND ND 5 * All composition hybrids can be obtained from CibaGdgy) 54 200406456 玖, description of the invention TMA data set in Table 7 indicates that the upper limit operating temperature of the polymorphic polymer composition is high For comparison of non-joined samples. Compare to, for example, Examples 21-2 to 21_3. The probe binding results indicate that the composition of the invention has an acceptable degree of binding, i.e., the probe binding value is at least 200 grams, more preferably at least 300 grams, and most preferably at least 380 grams. The G and Tg data indicate that polymorphic polymer compositions can be used in the composition of Inductive Adhesives, i.e., they are characterized by a G'105 to 106 dyneS / Cm2 and a Tg of -10 to 10. (: The examples in Table 7 show the flexibility of the technology of the invention, that is, the molecular weight and density of the main chain polymer and branched polymer can be changed to make the composition suitable for use in various pressure-sensitive adhesives. Examples 40-41: Adhesive samples functionalized to glass to prepare reactivity with polymers A10 and B4 (in the example of Example 40) and polymers A10 and D (in the example of Example 41) Co-extrusion. In each example, the polymer reactant was mixed by peroxide inhalation, and the inhaled sample was extruded in a twin-screw extruder at 21.0. Assess the higher processing temperature, shear surface adhesion, and τ_peel shear adhesion. The other surface shear adhesion system was determined by compression molding. The test resin was 35 ° F (177 °) in the glass of the second microscope. Between the slides, the slides were lined with gauze tape, and then a full-side shear adhesion test was performed on an Instron tensiometer. The τ-peel shear adhesion system was determined as follows. Glass slides (length, width, height: 3x1x 〇 〇 〇5 Inch (7.6 X 〇12αι〇 from Pisher Scientific) to cold spin Steel bar (CRS, length, width, height · 6χ ix 0.032 shots (15χ 2 · 5χ 〇 enough from Q-Panei CGmpany)-surface active agent in the 55 200406456 发明, invention description CRS bar and adhesive resin in glass On the sheet. Adequate mixing of the adhesive occurs when the slide and CRS are put together. The CRS / glass strip is placed on a hot plate (180 °. The HOPE-g-EO test polymer and the second metal strip are placed on top On a CRS / glass strip on a hot plate. They are heated until the polymer sample has dissolved. Then they are cooled to room temperature. These test samples are tested for 24 hours after preparation. The nominal pressure-tension diagram generation is used An Instron 4204 Materials Testing System according to ASIM method D1876-72 〇 The distance between the grips is 2 British pairs (5cra), and the crossover speed is 10 Ying / min (25cnymin) 〇 The polymorphic polymer composition and The properties of the finished product are set in the following Table 8. Consecrated BKphr) Poly-touch clear) Gathering Al_ Ιιρ®ο1130 Satoshi I ^ LT CQ Face chest contact Ti 丨 tender city green broken Xie Shengshi #gim)) HDPBg- B0 (2W) 25 75 05 120 25 (13¾ 〇 (〇) MAHg · HOEg. Β0 (14-2) 25 75 05 120 129 (112) 342 9) The polycrystalline polymer composition has a significantly increased adhesion to glass when it replaces HDPE as a branched polymer. The results in Table 8 show that the polymorphic composition of the polycrystalline form has a relatively high residual surface shear bonding and T-shear bonding compared to the non-functional polymorphic polymer composition. As discussed above with respect to the adhesive composition 21-9, the cis-butadiene-functional polymorphic polymer composition can be usefully used for pressure-sensitive adhesive composition. The present invention, which has been fully described and detailed above, should be based only on the scope of patent application below. 56 200406456 发明, description of the invention [Simplified description of the figure] Figure 1 shows the law of high temperature resistance of masses and impurities in the brain. 4 and Science Figure 2 Example of polymorphic polymer composition. Figure 3 shows that the polymorphic polymer compositions of Examples 20 and 21 endure a temperature before the hardness of support A decreases to 45 compared to Comparative Examples to 19. Figure 4 shows that the polymorphic polymer compositions of Examples 20 and 21 were penetrated by the probe to one side at a higher temperature than Comparative Example 19. Figure 5 shows a TEM image of Comparative Example 19. Figure 6 shows the "image" of the polymorphic polymer composition of Example 20. Figures 7 and 8 show the TEM images of Comparative Example 24 and Example 25 at 30,000 times magnification. [The main elements of the figure represent the symbol table 】no

57

Claims (1)

The invention claims a patented seed crystal type polymer composition, which is characterized by comprising: a homogeneous linear or homogeneous linear ethene / α-hydrocarbon interpolymer main chain; and a single blade attached to the main chain. This branch contains ethylene monomers or acetoolefin interpolymers with a density greater than 5 * of the primary bond and at least 0.004 g / cm3. 2. The polymorphic polymer composition as described in item i of the patent application, wherein the branch is characterized by containing a single element polymer with a density greater than that of the primary bond of at least 0.006 g / cm3. Smoke polymer. 10 3. The polymorphic polymer composition according to the scope of the patent application, wherein the polymer main chain is further characterized in that it is a simple linear or substantially linear interpolymerization composed of ethylene and at least one α-olefin. Property 04. The polymorphic polymer composition according to item 3 of the scope of patent application, wherein the 15 main chain homogeneous linear or substantially linear polymer is further characterized by having a CDBI value of at least 50 & Mw / Mn value Below 3. 5. The polymorphic polymer composition according to item 1 of the scope of patent application, wherein the polymer between the main chains is characterized by a substantially linear interpolymer having the following characteristics: 20% of melt flow ratio, I10 /I2g5.63, (b) —Molecular weight distribution, MVV / Mn is measured by gel permeation chromatography and defined by the following equation (Mw / Μη) $ (110/12) -4.63, …… (C ), At the total melting point. One of the starting points is critical. Shear pressure is squeezed in a morphology. Mpa) or a gaseous extrusion hydrodynamics such that the critical shear rate at the onset of melt fracture of the substantially linear ethylene interpolymer is at least 50% greater than the surface melting of a linear ethylene polymer The critical shear rate at the fracture initiation point, where the substantially linear ethylene polymer and the linear ethylene polymer contain the same comonomer. The linear ethylene polymer has a percentage of the substantially linear ethylene interpolymer. La, Mw /] VIn and density within ten, and wherein the substantially linear ethylene The critical shear rates of the interpolymer and the linear ethylene polymer were measured at the same melting temperature using a gaseous extrusion flow force meter, and (d) — a single differential scanning calorimeter, Dsc, with a melting peak at- Between 30 and 150 ° C. 6. The polymorphic polymer composition according to the scope of the patent application, wherein the interpolymer of the main chain is characterized in that it is substituted with a long-chain branch with an average value of 0.001 to 3 long chain / 1000 carbons. Substantially linear ethylene / α-olefin interpolymer. 7. The polymorphic polymer composition according to item 1 of the patent application scope, further characterized by comprising a molecular portion derived from a polar molecular portion bonded to at least one of the main chain polymer or the branched polymer. 8 · —A method for preparing a polymorphic polymer composition as described in the scope of the patent application ', wherein the method is characterized by comprising: (a) polymerizing ethylene and optionally one or more under reaction conditions Olefins are used to form a branch-forming polymer; and 59 200406456, the scope of patent application (b) polymerizes ethylene, or a plurality of monomers under reaction conditions, and (a) the branch-forming polymerization To form the polymorphic polymer composition; wherein the polymorphic polymer composition is characterized by having a main chain polymer portion and an additional branched polymer portion, wherein the branched polyliths are separated at room temperature The degree of crystallinity is at least 5 percent greater than the backbone polymer portion. 9. The method of claim 8 in the scope of patent application, wherein ("the polymerization reaction occurs in the first reactor and (b) the polymerization reaction occurs in a second reactor, or (a) the polymerization reaction occurs in In the same reactor as the polymerization reaction (13), and wherein a first catalyst is used during the polymerization reaction and a second compatible catalyst is used during the polymerization reaction of (b). 15 10 · —Type A method for preparing a polymorphic polymer composition according to item 1 of the scope of the patent application, wherein the method is characterized by comprising: (a) polymerizing ethyl glutamate and optionally one or more α-foam under the reaction conditions; Comonomers to form a reaction vapor comprising a branched polymer; 20 (b) polymerizing ethylene and one or more alpha-olefin comonomers to form a polymer comprising a homogeneous linear or substantially linear backbone Reaction vapor, (c) optionally isolating (a) the branch-forming polymer of the reaction vapor and (b) the backbone-forming polymer of the reaction vapor, and (d) a radical initiation In the presence of matter He 60 200406456 Pick up and apply for a patent for the foam enclosure and the polymer forming the main chain, so that the branched polymer is attached to the polymer forming the main chain to make the polymorphic polymer composition; 纟The branch-forming polymer has-the degree of crystallinity at room temperature of 5 is at least 5 percent greater than the degree of crystallinity of the polymer forming the main chain. Η · The method of item (i) of the patent, wherein this step ⑷ The reaction occurs before the branching polymer and the polymer forming the main chain are isolated from the reaction vapor in (a) and ⑻, and the method further includes: 单 detaching the poly from the reaction vapor in the self-binding reaction Crystalline polymer composition. 10I2. The polycrystalline polymer composition according to item 1 of the scope of patent application, which is a -adhesive, sealant, coating agent, casting part, diaphragm, thermoformed part. Or in the form of fibers. 13. A hot melt adhesive formulation comprising a polymorphic composition as described in the scope of the patent application. 15 14 · A hot melt adhesive formulation 'comprising a polymorphic polymer composition Substance, wherein the polymorphic polymer The product is characterized by containing a reaction product consisting of: (a) a branching polymer from 40 to 5 weight percent, the branch comprising an ethylene simple polymer or an ethylene olefin interpolymer, and (b ) 20 substances that form a primary bond from one of 60 to 95 percent by weight, which is ethylene or one or more comonomers or which is a homogeneous linear or substantially linear ethylene / α-olefin interpolymer; and the branches shaped therein The degree of crystallinity is at least 5 percent greater than the crystallinity of the main chain formed; and ... the polycrystalline polymer composition has an upper limit operating temperature of 61 200406456 0 '.--· ; *-· Pick up and apply for a patent with a range of at least 10 ° c greater than an unreacted blend composed of the branched polymer and the main chain polymer formed. 15. The hot melt adhesive formulation according to item 13 or 14 of the patent application scope, which is characterized by having a probe binding system of at least 200 grams and an upper operating temperature of at least HTC greater than The temperature of the hot-melt adhesive consisting of a branched polymer and an unreacted blend of the main = polymer provided in an amount equal to the amount of the polycrystalline polymer composition 10 62