Polyolefin wax, resin composition, coating agent and adhesive

Abstract

To provide a polyolefin wax which is excellent in solubility and handleability, a resin composition containing the polyolefin wax, a coating agent containing the polyolefin wax, and an adhesive containing the polyolefin wax.SOLUTION: A polyolefin wax includes a constitutional unit derived from propylene and a constitutional unit derived from 1-butene. A content ratio of the constitutional unit derived from the propylene is 60 mol% to 95 mol%. A content ratio of the constitutional unit derived from the 1-butene is 5 mol% to 40 mol%. The melting point is lower than 105°C. The weight average molecular weight (Mw) is 3,000 to 70,000. The number of terminal unsaturated bond amounts per 1,000 pieces of carbon atoms, which is measured by 1HNHR, is 1 piece or less. The stereoregularity index, which is measured by 13CNMR, is 85% or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polyolefin wax, a resin composition, a coating agent, and an adhesive, and more particularly to a polyolefin wax, a resin composition containing the polyolefin wax, a coating agent containing the polyolefin wax, and an adhesive containing the polyolefin wax. [Background technology]

[0002] Acid-modified polyolefin waxes have been known as dispersants, and by blending such acid-modified polyolefin waxes with a resin composition containing a filler, the dispersibility of the filler can be improved.

[0003] The acid-modified polyolefin wax can be obtained, for example, by modifying a polyolefin wax with an acid.

[0004] As the polyolefin wax, for example, a polyolefin wax which is a copolymer of ethylene and propylene has been proposed (for example, Patent Document 1).

[0005] Furthermore, as a polyolefin elastomer, for example, a polypropylene-based elastomer which is a copolymer of propylene and 1-butene and has an intrinsic viscosity of 1.82 dl / g has been proposed (for example, Example 1 of Patent Document 2).

[0006] In addition, as a polyolefin wax, for example, a propylene-α-olefin copolymer (low molecular weight) obtained by thermally decomposing a propylene-α-olefin copolymer (high molecular weight) having 4 or more carbon atoms has been proposed (for example, Patent Document 3). [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 06-049129 [Patent Document 2] Japanese Patent Application Laid-Open No. 2004-099909 [Patent Document 3] International Publication No. 2013 / 146605 Brochure Summary of the Invention [Problem to be solved by the invention]

[0008] On the other hand, the polyolefin wax of Patent Document 1 has the drawback of low solubility.

[0009] Furthermore, the polypropylene elastomer of Patent Document 2 has a high intrinsic viscosity (in other words, a high molecular weight), and therefore, when such a polypropylene elastomer is dissolved in a solvent, the viscosity becomes high, which causes the problem of poor handleability.

[0010] In addition, in Patent Document 3, a low-molecular-weight propylene-α-olefin copolymer is produced by thermally decomposing the molecular chain of a high-molecular-weight polymer (propylene-α-olefin copolymer having 4 or more carbon atoms), but the propylene-α-olefin copolymer obtained by thermal decomposition has a large amount of unsaturated bonds at its molecular terminals. Therefore, when the propylene-α-olefin copolymer of Patent Document 3 is modified with an acid, the viscosity increases, which makes it difficult to handle.

[0011] The present invention provides a polyolefin wax having excellent solubility and handleability, a resin composition containing the polyolefin wax, a coating agent containing the polyolefin wax, and an adhesive containing the polyolefin wax. [Means for solving the problem]

[0012] The present invention [1] comprises structural units derived from propylene and structural units derived from 1-butene, the content of the structural units derived from propylene is 60 mol% to 95 mol%, the content of the structural units derived from 1-butene is 5 mol% to 40 mol%, the melting point is less than 105°C, and the weight average molecular weight (Mw) is 3,000 to 70,000, 1 The number of terminal unsaturated bonds per 1000 carbon atoms measured by HNHR is 1 or less, 13 It is a polyolefin wax having a stereoregularity index of 85% or more as measured by CNMR.

[0013] The present invention [2] includes the polyolefin wax according to the above [1], which has a molecular weight dispersity (Mw / Mn) of 3.0 or less.

[0014] The present invention [3] includes the polyolefin wax according to the above [1] or [2], which has a melting point of 80°C to 100°C.

[0015] The present invention [4] comprises the polyolefin wax according to any one of the above [1] to [3], which has a weight average molecular weight (Mw) of 10,000 to 65,000.

[0016] The present invention [5] is 13 The polyolefin wax according to any one of the above [1] to [4] has a stereoregularity index of more than 90% as measured by CNMR.

[0017] The present invention [6] contains the polyolefin wax according to any one of the above [1] to [5], in which the content of the structural units derived from propylene is 70 mol% to 88 mol% and the content of the structural units derived from 1-butene is 12 mol% to 30 mol%.

[0018] The present invention [7] comprises the polyolefin wax according to any one of the above [1] to [6], which has a half-width of the crystalline melting point peak measured by a differential scanning calorimeter of 1.0°C to 20.0°C.

[0019] The present invention [8] includes a resin composition containing the polyolefin wax according to any one of the above [1] to [7].

[0020] The present invention [9] includes a coating agent containing the polyolefin wax according to any one of the above [1] to [7].

[0021] The present invention

[10] includes an adhesive containing the polyolefin wax according to any one of the above [1] to [7]. [Effects of the Invention]

[0022] The polyolefin wax of the present invention contains a predetermined proportion of structural units derived from propylene and a predetermined proportion of structural units derived from 1-butene, thereby improving solubility.

[0023] In addition, the melting point of the polyolefin wax is less than 105° C., which improves solubility.

[0024] Furthermore, the weight average molecular weight (Mw) of the polyolefin wax is 3,000 to 70,000. This improves the ease of handling.

[0025] In addition, in the polyolefin wax, 1 The number of terminal unsaturated bonds per 1000 carbon atoms, as measured by HNHR, is 1 or less. This makes it less likely to thicken during acid modification, improving handleability.

[0026] In addition, in the polyolefin wax, 13The stereoregularity index measured by CNMR is 85% or more. Therefore, when designing a low melting point, the 1-butene content can be increased, which results in a material with a narrow half-width, improving solubility.

[0027] The resin composition of the present invention contains the polyolefin wax of the present invention, and therefore, the solubility and handling properties can be improved.

[0028] The coating agent of the present invention contains the polyolefin wax of the present invention, which can improve solubility and handling properties.

[0029] The adhesive of the present invention contains the polyolefin wax of the present invention, which can improve solubility and handling properties. DETAILED DESCRIPTION OF THE INVENTION

[0030] <Polyolefin wax> The polyolefin wax contains structural units derived from propylene and structural units derived from 1-butene.

[0031] Such polyolefin waxes are polymers of polymerization components including propylene and 1-butene.

[0032] The polymerization components essentially comprise propylene and 1-butene.

[0033] The polymerization components may optionally contain other monomers. When the polymerization components contain other monomers, the polyolefin wax contains structural units derived from the other monomers.

[0034] Examples of the other monomers include ethylene and α-olefins having 5 or more carbon atoms. Examples of the α-olefins having 5 or more carbon atoms include 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 1-dodecene.

[0035] The other monomers can be used alone or in combination of two or more kinds.

[0036] Furthermore, as the monomers of the polymerization components, for example, monomers derived from fossil fuels and / or monomers derived from biomass can be used. Specifically, as the monomers of the polymerization components, a fossil fuel-derived monomer can be used alone, a biomass-derived monomer can be used alone, or a combination of a fossil fuel-derived monomer and a biomass-derived monomer can be selected.

[0037] Fossil fuels are oil, coal, natural gas, shale gas, or combinations thereof. Biomass is any renewable natural raw material and its residues, such as from plants or animals, including fungi, yeasts, algae, and bacteria.

[0038] The polymerization components preferably contain no other monomers and include propylene and 1-butene, i.e., the polyolefin wax preferably consists of a copolymer of propylene and 1-butene.

[0039] In the polyolefin wax, the content of structural units derived from propylene is 60 mol% to 95 mol%, and from the viewpoint of further improving solubility, it is preferably 70 mol% to 88 mol%, and more preferably 72 mol% to 80 mol%.

[0040] When the content of the structural units derived from propylene is within the above range, the solubility can be improved.

[0041] On the other hand, if the content of the structural units derived from propylene is outside the above range, the solubility decreases.

[0042] In addition, the content of structural units derived from 1-butene in the polyolefin wax is 5 mol% to 40 mol%, and from the viewpoint of further improving solubility, it is preferably 12 mol% to 30 mol%, and more preferably 20 mol% to 28 mol%.

[0043] When the content of the structural units derived from 1-butene is within the above range, the solubility can be improved.

[0044] On the other hand, if the content of structural units derived from 1-butene is outside the above range, the solubility decreases.

[0045] The method for measuring the content ratio of the structural units derived from propylene and the structural units derived from 1-butene will be described in detail in the Examples below.

[0046] <Method of manufacturing polyolefin wax> The polyolefin wax can be obtained by polymerizing the polymerization components in the presence of an olefin polymerization catalyst.

[0047] The olefin polymerization catalyst comprises a transition metal compound.

[0048] Examples of the transition metal compound include the transition metal compounds listed in WO 2014 / 050816.

[0049] The transition metal compound is preferably a transition metal compound represented by the following general formula (1). [ka]

[0050] The olefin polymerization catalyst preferably comprises an organoaluminum compound.

[0051] Examples of organoaluminum compounds include trialkylaluminum, dialkylaluminum hydride, and tricycloalkylaluminum. Examples of trialkylaluminums include trimethylaluminum, triethylaluminum, and triisobutylaluminum. Examples of dialkylaluminum hydrides include diisobutylaluminum hydride.

[0052] As the organoaluminum compound, preferably, trialkylaluminum is used, and more preferably, triisobutylaluminum is used.

[0053] The organoaluminum compounds can be used alone or in combination of two or more.

[0054] The polymerization method is preferably solution polymerization.

[0055] In solution polymerization, the polymerization components are polymerized in the presence of a solvent (e.g., cyclohexane, n-hexane). Preferably, the polymerization components and an olefin polymerization catalyst (a transition metal compound and, if necessary, an organoaluminum compound) are continuously supplied to the solvent in a reaction vessel to polymerize the polymerization components continuously. Preferably, propylene and 1-butene are supplied in liquid form.

[0056] The supply amount of propylene is, for example, 0.1 L / hour to 10.0 L / hour, or preferably 0.5 L / hour to 5.0 L / hour.

[0057] The supply amount of 1-butene is smaller than the supply amount of propylene, and is, for example, 0.10 L / hour to 4.00 L / hour, preferably 0.20 L / hour to 3.00 L / hour, and more preferably 0.30 L / hour to 1.00 L / hour.

[0058] The solvent supply rate is, for example, 0.50 L / hour to 50 L / hour, preferably 1.00 L / hour to 10 L / hour, and more preferably 2.00 L / hour to 5.00 L / hour.

[0059] The supply amount of the transition metal compound is, for example, 0.0010 mmol / hour to 0.3000 mmol / hour, preferably 0.0020 mmol / hour to 0.1000 mmol / hour, more preferably 0.0030 mmol / hour to 0.0100 mmol / hour, and even more preferably 0.0040 mmol / hour to 0.0070 mmol / hour.

[0060] The supply amount of the organoaluminum compound is, for example, 0.1 mmol / hour to 10 mmol / hour, preferably 0.5 mmol / hour to 5.0 mmol / hour, more preferably 1.0 mmol / hour to 3.0 mmol / hour, and even more preferably 1.5 mmol / hour to 2.0 mmol / hour.

[0061] The molar ratio of the organoaluminum compound to the transition metal compound (organoaluminum compound / transition metal compound) is, for example, 10-1000, preferably 15-100, more preferably 20-40, and still more preferably 25-35.

[0062] The polymerization temperature is, for example, 60°C to 170°C, preferably 80°C to 150°C, more preferably 90°C to 130°C, and still more preferably 100°C to 120°C.

[0063] The polymerization pressure is, for example, 0.1 MPa to 10.0 MPa, preferably 1.0 MPa to 5.0 MPa, and more preferably 2.0 MPa to 4.0 MPa.

[0064] In this method, hydrogen is supplied to adjust the molecular weight, which can lower the weight average molecular weight of the polyolefin wax.

[0065] The amount of hydrogen supplied is, for example, 1.0 NL / hour to 50.0 NL / hour, preferably 5.0 NL / hour to 30.0 NL / hour, and more preferably 10.0 NL / hour to 20.0 NL / hour.

[0066] The amount of polyolefin wax extracted is, for example, 10 g / hour to 1000 g / hour, or preferably 100 g / hour to 500 g / hour.

[0067] This produces a polyolefin wax.

[0068] <Physical properties of polyolefin wax> The melting point of the polyolefin wax is less than 105°C, and from the viewpoint of further improving solubility, it is preferably 100°C or less, more preferably 95°C or less, even more preferably 90°C or less, and for example, 40°C or more, preferably 50°C or more, and from the viewpoint of mechanical strength and adhesiveness, it is more preferably 60°C or more, even more preferably 70°C or more, particularly preferably 80°C or more.

[0069] When the melting point of the polyolefin wax is less than the upper limit, the solubility can be improved.

[0070] On the other hand, if the melting point of the polyolefin wax is above the upper limit, the solubility decreases.

[0071] The melting point of the polyolefin wax can be measured by a differential scanning calorimeter.

[0072] In the polyolefin wax, the half width of the crystalline melting point peak measured by a differential scanning calorimeter is, for example, 1.0°C to 20.0°C, preferably 5.0°C to 15.0°C, more preferably 7.0°C to 10.0°C, and even more preferably 8.0°C to 9.0°C.

[0073] Specifically, in the polyolefin wax, the half-value width of the crystalline melting point peak measured by a differential scanning calorimeter is, for example, 20.0°C or less, preferably 15.0°C or less, more preferably 10.0°C or less, and even more preferably 9.0°C or less, from the viewpoint of further improving solubility.

[0074] The weight average molecular weight (Mw) of the polyolefin wax is 3,000 to 70,000, preferably 10,000 to 65,000, more preferably 20,000 to 60,000, still more preferably 30,000 to 55,000, and particularly preferably 40,000 to 50,000.

[0075] Specifically, the weight average molecular weight (Mw) of the polyolefin wax is 3,000 or more, preferably 10,000 or more, more preferably 20,000 or more, even more preferably 30,000 or more, particularly preferably 40,000 or more, and 70,000 or less, preferably 65,000 or less, more preferably 60,000 or less, even more preferably 55,000 or less, particularly preferably 50,000 or less.

[0076] When the weight average molecular weight (Mw) of the polyolefin wax is equal to or higher than the above lower limit, the mechanical strength can be improved.

[0077] On the other hand, if the weight average molecular weight (Mw) of the polyolefin wax is less than the above lower limit, the mechanical strength decreases.

[0078] Furthermore, when the weight average molecular weight (Mw) of the polyolefin wax is equal to or less than the above upper limit, the handleability can be improved.

[0079] On the other hand, if the weight average molecular weight (Mw) of the polyolefin wax exceeds the upper limit, the handling property decreases.

[0080] The weight average molecular weight (Mw) is a polystyrene-equivalent molecular weight determined by gel permeation chromatography (GPC).

[0081] The number average molecular weight (Mn) of the polyolefin wax is, for example, 1,000 to 45,000, preferably 3,000 to 36,000, more preferably 6,000 to 30,000, and still more preferably 10,000 to 25,000.

[0082] Specifically, the number average molecular weight (Mn) of the polyolefin wax is, from the viewpoint of improving mechanical strength, for example, 1,000 or more, preferably 3,000 or more, more preferably 6,000 or more, and even more preferably 10,000 or more. From the viewpoint of improving handleability, it is, from the viewpoint of improving handleability, 45,000 or less, preferably 36,000 or less, and more preferably 30,000 or less. More preferably, it is 25,000 or less.

[0083] The number average molecular weight (Mn) is a polystyrene-equivalent molecular weight determined by gel permeation chromatography (GPC).

[0084] The molecular weight dispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the polyolefin wax is, for example, 3.0 or less, preferably 2.5 or less, more preferably 2.2 or less, and for example, 1.5 or more.

[0085] When the molecular weight dispersity of the polyolefin wax is equal to or less than the upper limit, the adhesive strength can be improved.

[0086] In polyolefin wax, 1 The number of terminal unsaturated bonds per 1000 carbon atoms measured by HNHR is 1 or less, preferably 0.5 or less, and more preferably 0.1 or less.

[0087] When the number of terminal unsaturated bonds is equal to or less than the upper limit, the increase in viscosity during acid modification is small, and handling properties can be improved.

[0088] On the other hand, if the number of terminal unsaturated bonds exceeds the upper limit, the viscosity increases significantly during acid modification, and handling becomes difficult.

[0089] The method for measuring the number of terminal unsaturated bonds will be described in detail in the Examples below.

[0090] In polyolefin wax, 13 The stereoregularity index (mm) measured by CNMR is 85% or more, preferably 90% or more, more preferably more than 90%, even more preferably 91% or more, particularly preferably 92% or more, and for example, 99% or less.

[0091] When the stereoregularity index is equal to or greater than the lower limit, the 1-butene content can be increased, thereby obtaining a material with a narrow half-value width, thereby improving solubility.

[0092] On the other hand, if the stereoregularity index is less than the lower limit, the half-value width becomes broad and the material contains a high-melting point component, resulting in a decrease in solubility.

[0093] The method for measuring the stereoregularity index will be described in detail in the examples below.

[0094] From the viewpoint of handleability, the melt viscosity (180°C) of the polyolefin wax is, for example, 30,000 mPa·s or less, preferably 20,000 mPa·s or less, more preferably 15,000 mPa·s or less, even more preferably 10,000 mPa·s or less, particularly preferably 5,000 mPa·s or less, and for example, 100 mPa·s or more.

[0095] The melt viscosity can be measured by a Brookfield viscometer.

[0096] Polyolefin waxes have excellent solubility and ease of handling, and are therefore suitable as additives for resin compositions, coating agents, and adhesives. That is, the resin compositions, coating agents, and adhesives contain polyolefin waxes.

[0097] Specifically, when polyolefin wax is used as an additive, the polyolefin wax may first be dissolved in a known solvent (for example, methylcyclohexane) to prepare a polyolefin wax solution.

[0098] On the other hand, polyolefin wax has excellent solubility and can be easily dissolved in known solvents.

[0099] Furthermore, the viscosity of the polyolefin wax solution can be prevented from increasing excessively, resulting in excellent handling properties.

[0100] If necessary, the polyolefin wax is modified with an unsaturated carboxylic acid to produce an acid-modified polyolefin wax.

[0101] The unsaturated carboxylic acid may, for example, be an unsaturated carboxylic acid having 3 to 8 carbon atoms. Examples of unsaturated carboxylic acids having 3 to 8 carbon atoms include monobasic acids and dibasic acids. Examples of monobasic acids include (meth)acrylic acid (acrylic acid and / or methacrylic acid), crotonic acid, and isocrotonic acid. Examples of dibasic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, allyl succinic acid, nadic acid, methyl nadic acid, tetrahydrofumaric acid, and methyl hexahydrophthalic acid.

[0102] Furthermore, examples of the unsaturated carboxylic acid include acid anhydrides of the above-mentioned unsaturated carboxylic acids.

[0103] The unsaturated carboxylic acid is preferably an acid anhydride of an unsaturated carboxylic acid. The unsaturated carboxylic acid is more preferably an acid anhydride of a dibasic acid. The unsaturated carboxylic acid is further preferably maleic anhydride.

[0104] The unsaturated carboxylic acids can be used alone or in combination of two or more kinds.

[0105] The acid-modified polyolefin wax can be obtained by reacting the polyolefin wax with an unsaturated carboxylic acid, in which the unsaturated carboxylic acid is grafted onto the polyolefin wax.

[0106] Specifically, first, the polyolefin wax is melted at, for example, 100°C or higher, preferably 150°C or higher, and, for example, 180°C or lower.

[0107] Next, maleic anhydride and a radical polymerization initiator are added, and the mixture is heated and stirred.

[0108] The mixing ratio of maleic anhydride relative to 100 parts by mass of the polyolefin wax is, for example, 1 part by mass or more, preferably 5 parts by mass or more, and for example, 15 parts by mass or less, preferably 8 parts by mass or less.

[0109] The radical polymerization initiator may, for example, be an organic peroxide (for example, di-tert-butyl peroxide).

[0110] The mixing ratio of the radical polymerization initiator relative to 100 parts by mass of the polyolefin wax is, for example, 1 part by mass or more, and for example, 5 parts by mass or less, preferably 3 parts by mass or less.

[0111] The radical polymerization initiators can be used alone or in combination of two or more kinds.

[0112] Regarding the heating conditions, the heating temperature is, for example, 100° C. or more, preferably 150° C. or more, and for example, 200° C. or less, preferably 180° C. or less. The heating time is, for example, 0.5 hours or more, and for example, 6 hours or less.

[0113] In this way, an acid-modified polyolefin wax is produced.

[0114] <Action and effect> The polyolefin wax contains a specific proportion of structural units derived from propylene and a specific proportion of structural units derived from 1-butene, which can improve solubility.

[0115] Furthermore, the melting point of polyolefin wax is less than 105° C., which improves solubility.

[0116] Furthermore, the weight-average molecular weight (Mw) of the polyolefin wax is 3,000 to 70,000. This improves the ease of handling. Specifically, when the polyolefin wax is dissolved in a known solvent to prepare a polyolefin wax solution, the viscosity of the polyolefin wax solution can be prevented from increasing excessively, improving the ease of handling.

[0117] In addition, in this polyolefin wax, 1 The number of terminal unsaturated bonds per 1000 carbon atoms measured by HNHR is 1 or less. This improves handleability. Specifically, when a polyolefin wax is modified with an acid (unsaturated carboxylic acid), if the number of terminal unsaturated bonds is large, a crosslinking reaction with the acid may proceed, resulting in an excessive increase in viscosity and a decrease in handleability.

[0118] In particular, in Patent Document 3, a low-molecular-weight propylene-α-olefin copolymer is produced by pyrolyzing the molecular chain of a high-molecular-weight polymer (propylene-α-olefin copolymer having 4 or more carbon atoms), but the propylene-α-olefin copolymer obtained by pyrolysis has a large amount of unsaturated bonds at its molecular terminals. Therefore, when the propylene-α-olefin copolymer of Patent Document 3 is modified with an acid, the viscosity increases excessively, resulting in poor handleability.

[0119] On the other hand, in this polyolefin wax, the number of terminal unsaturated bonds is not more than 1. Therefore, the crosslinking reaction can be suppressed, an excessive increase in viscosity can be suppressed, and handling properties can be improved.

[0120] In addition, in the polyolefin wax, 13 The stereoregularity index measured by CNMR is 85% or more. Therefore, by increasing the 1-butene content, the material has a low melting point and a narrow half-width, which improves solubility.

[0121] The resin composition contains a polyolefin wax, which can improve solubility and handling.

[0122] The coating agent contains polyolefin wax, which improves solubility and handling.

[0123] The adhesive contains a polyolefin wax, which improves solubility, handling, and adhesive strength. [Example]

[0124] Next, the present invention will be described based on examples and comparative examples, but the present invention is not limited to the following examples. Note that "parts" and "%" are by mass unless otherwise specified. Furthermore, specific numerical values ​​such as blending ratios (content ratios), physical property values, and parameters used in the following description can be substituted with the corresponding upper limit values ​​(numeric values ​​defined as "equal to or less than") or lower limit values ​​(numeric values ​​defined as "equal to or more than" or "exceeding") of the blending ratios (content ratios), physical property values, parameters, etc. described in the above "Modes for Carrying Out the Invention."

[0125] <Production of polyolefin wax> Examples 1 to 5 and Comparative Examples 1 to 4 Olefins were produced by polymerizing the polymerization components in the presence of an olefin polymerization catalyst. Specifically, a pressure-resistant reactor (internal volume 100 L) equipped with a temperature-controllable jacket and agitator blades was used. The polymerization components (propylene (liquid), 1-butene (liquid), and ethylene (gas)) and hydrogen were continuously supplied to a solvent (n-hexane) containing the olefin polymerization catalyst under the polymerization conditions listed in Table 1, to polymerize the polymerization components. The olefin polymerization catalyst used was a transition metal compound of the general formula (1) above and triisobutylaluminum (an organoaluminum compound). The transition metal compound of the general formula (1) above was synthesized by a method similar to Example 1A described in International Publication No. 2014 / 050816. A polyolefin wax was thus produced.

[0126] Comparative Example 5 A 2000 ml polymerization reactor, thoroughly purged with nitrogen, was charged with 900 ml of dry hexane, 65 g of 1-butene, and triisobutylaluminum (1.0 mmol) at room temperature. The temperature inside the reactor was then raised to 70 °C and pressurized to 0.7 MPa with propylene. A toluene solution containing 0.002 mmol of dimethylmethylene(3-tert-butyl-5-methylcyclopentadienyl)fluorenylzirconium dichloride and 0.6 mmol of methylaluminoxane (Tosoh Finechem Corporation) (calculated as aluminum) was then added to the polymerization reactor. Polymerization was carried out for 30 minutes while maintaining an internal temperature of 62 °C and a propylene pressure of 0.7 MPa. The polymerization was terminated by the addition of 20 ml of methanol. After depressurization, the polymer was precipitated from the polymerization solution in 2 L of methanol and dried under vacuum at 130 °C for 12 hours. This produced a polyolefin wax.

[0127] Comparative Example 6 200 g of the polyolefin wax of Comparative Example 5 was placed in a 1.5 L stainless steel pyrolyzer equipped with a stirrer, a nitrogen inlet tube, and a condenser, and the atmosphere was thoroughly replaced with nitrogen. Next, the pyrolyzer was heated to 380°C while nitrogen was still flowing in, and the polyolefin wax was melted, after which stirring was started. After the temperature of the polyolefin wax reached the predetermined temperature, the polyolefin wax was heated for 4.5 hours to carry out pyrolysis. The pyrolyzer was then cooled to room temperature. A polyolefin wax (pyrolyzed product) was obtained.

[0128] Comparative Example 7 As the polyolefin wax, Elmodu™ S600 (low stereoregularity PP) manufactured by Idemitsu Kosan Co., Ltd. was used as it was.

[0129] <Evaluation> [Structural units derived from propylene, structural units derived from 1-butene, and structural units derived from ethylene] The C-NMR spectrum of each polyolefin wax of each example and comparative example was measured. Specifically, 60 mg of the sample was completely dissolved in 0.6 ml of o-dichlorobenzene / deuterated benzene (4 / 1 v / v) in an NMR sample tube, and then measured at 120°C using a JEOL ECA500 nuclear magnetic resonance spectrometer. [Propylene content] Each peak was assigned in accordance with a conventional method, and the contents of the structural units derived from propylene, 1-butene, and ethylene were calculated based on the following formulas (1) to (6). The results are shown in Table 1. The propylene content was calculated from the relationship between the composition and the dyad chain using the main chain methylene carbon. Propylene-ethylene copolymer P=PP+1 / 2PE(1) E=EE+1 / 2PE(2) Propylene content (mol%) = P / (P+E) × 100 (3) Propylene-1-butene copolymer P=PP+1 / 2PB(4) B=BB+1 / 2PB(5) Propylene content (mol%) = P / (P+B) × 100 (6) P: Propylene ratio, E: Ethylene ratio, B: 1-butene ratio PP, PE, EE, PB, BB: Proportion of each dyad chain [Tacticity (mm, triad fraction)] The peak intensities of the syndiotactic rr (19.0-20.5 ppm), heterotactic mr (20.5-21.2 ppm), and isotactic mm (21.2-22.5 ppm) were determined from the methyl group-derived signals between 19.0 and 22.5 ppm, and the stereoregularity (mm, triad fraction) was calculated from the ratio of these peak intensities. The results are shown in Table 1.

[0130] [Weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight dispersity (Mw / Mn)] The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight dispersity (Mw / Mn) of the polyolefin waxes of each Example and Comparative Example were determined. Specifically, GPC measurements were performed under the following conditions, and the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight dispersity (Mw / Mn) were determined from a calibration curve using commercially available monodisperse standard polystyrene. The results are shown in Table 1. {conditions} Apparatus: Gel permeation chromatograph HLC-8321GPC·HT (Tosoh Corporation) Solvent: o-Dichlorobenzene (Wako Pure Chemical Industries, Ltd., special grade reagent, contains 0.025% dibutylhydroxytoluene (stabilizer)) Columns: Two TSKgel GMH6-HT columns and two TSKgel GMH6-HTL columns (inner diameter 7.5 mm x length 30 cm, Tosoh Corporation) connected in series Flow rate: 1.0ml / min Sample: 0.1 mg / mL o-dichlorobenzene solution Column temperature: 140℃ Injection volume: 400μl Detector: differential refractometer Sampling time interval: 0.5 seconds

[0131] [Melting point and crystalline melting point peak half-width] The melting point and half-width of the crystalline melting point peak of each polyolefin wax in each example and comparative example were measured using a DSC (DSC-7200) manufactured by Hitachi High-Tech.

[0132] Specifically, approximately 5 mg of polyolefin wax was sampled and filled into a TA Instruments Hermtic Lid (900794.901) / Hermetic Pan (900793.901) to prepare a sample. The sample was then heated to 200°C under a nitrogen atmosphere, held for 5 minutes, and then cooled to 30°C at 10°C / min. The sample was then held at 30°C under a nitrogen atmosphere for 5 minutes, and then heated to 230°C at 10°C / min. The melting point was determined from the peak apex of the crystalline melting peak observed at this time. The half-width was also calculated from the difference between the high-temperature and low-temperature temperatures at which half the intensity of the peak apex was obtained. The results are shown in Table 1.

[0133] [Number of terminal unsaturated bonds per 1000 carbon atoms] Regarding the polyolefin waxes of each example and each comparative example, 1 The number of terminal unsaturated bonds per 1,000 carbon atoms was determined using HNHR (Bruker Biospin AVANCE IIIcryo-500 nuclear magnetic resonance spectrometer). Specifically, 20 mg of polyolefin wax was completely dissolved in approximately 0.6 ml of deuterated o-dichlorobenzene in an NMR sample tube (5 mm diameter) and measured at 120 °C. The total integrated intensity of the propylene-derived signal was normalized to 20,000. The integrated intensities of the three-proton peaks derived from vinyl groups observed near 4.7 ppm and 5.7 ppm and the two-proton peak derived from vinylidene groups observed near 4.5 ppm were used to calculate the vinyl and vinylidene amounts using the following equation (4). The sum of these values ​​was used to determine the amount of terminal unsaturated bonds. The results are shown in Table 1. Amount of terminal unsaturated bonds (units / 1000 carbon atoms) = (integrated intensity of peaks derived from vinyl groups) / 30 + (integrated intensity of the peak derived from the vinylidene group) / 20 (4)

[0134] [Melt viscosity] The polyolefin waxes of each of the Examples and Comparative Examples were heated to 180° C. to melt them, and their viscosities were measured by the following method.

[0135] That is, the melt viscosity was measured at 180° C. using a Brookfield B-type viscometer (model number DV-II+). The results are shown in Table 1.

[0136] [Solubility] The polyolefin wax of each Example and Comparative Example and methylcyclohexane (MCH) were added to a vial so that the total amount was 20 g (2 g for 10 mass % polyolefin wax and 4 g for 20 mass % polyolefin wax).

[0137] Next, a stirrer was placed in the vial, and the polyolefin wax was dissolved in the MCH while stirring with a hot plate stirrer at 80°C for 30 minutes at 150 rpm to prepare a polyolefin wax solution.

[0138] The samples were then left to stand at room temperature (23°C) for one week. The solubility was evaluated based on the following criteria. For polyolefin waxes whose solubility was evaluated as "◎", "○" or "△", the viscosity at 23°C was measured using a Brookfield viscometer. The results are shown in Table 1. {standard} ⊚: The solution state was maintained. The polyolefin wax solution was transparent. ◯: The solution state was maintained. The polyolefin wax solution became cloudy. △: Partial solidification occurred after standing for 1 week. ×: Solidified within 3 days of standing.

[0139] [Handling when acid-denatured] A glass reactor was charged with 800 g of the polyolefin wax from each Example and Comparative Example and melted at 170°C under a nitrogen atmosphere. Next, 42 g of maleic anhydride and 8.8 g of a radical polymerization initiator were continuously fed to the reaction system (temperature: 170°C) over 5 hours. After heating and reacting for 1 hour, the molten wax was degassed for 0.5 hours under a vacuum of 10 mmHg to remove volatiles. The reaction mixture was then cooled to obtain an acid-modified polyolefin wax. Next, GPC measurement was performed, and the weight-average molecular weight (Mw) was determined from a calibration curve using commercially available monodisperse standard polystyrene. It can be seen that the smaller the weight-average molecular weight, the better the handling properties during acid modification. The results are shown in Table 1.

[0140] <Consideration> Examples 1 to 3 and Comparative Example 1 have similar melting points. When compared at similar melting points, Examples 2 to 5, which contain a predetermined proportion of structural units derived from propylene and a predetermined proportion of structural units derived from 1-butene, are found to have superior solubility compared to Comparative Example 1, which does not contain any structural units derived from 1-butene. This is also true when Examples 4 and 5 are compared with Comparative Example 2. Furthermore, Examples 1 to 3 and Comparative Example 3 have similar melting points. When compared at similar melting points, Comparative Example 1 has a higher viscosity than Examples 1 to 3 in the solubility evaluation. This shows that Examples 1 to 3 are superior in handleability compared to Comparative Example 1. This is also true when Examples 4 and 5 are compared with Comparative Example 4.

[0141] [Table 1]

Claims

1. Contains structural units derived from propylene and structural units derived from 1-butene, the content ratio of the structural units derived from propylene is 60 mol% to 95 mol%, the content ratio of the structural units derived from 1-butene is 5 mol% to 40 mol%; The melting point is less than 105°C, The weight average molecular weight (Mw) is 3,000 to 70,000, １ the number of terminal unsaturated bonds per 1000 carbon atoms is 1 or less as measured by HNMR; １３ A polyolefin wax having a stereoregularity index of 85% or more as measured by CNMR.

2. The polyolefin wax according to claim 1, having a molecular weight dispersity (Mw / Mn) of 3.0 or less.

3. 2. The polyolefin wax according to claim 1, which has a melting point of 80°C to 100°C.

4. The polyolefin wax according to claim 1, having a weight average molecular weight (Mw) of 10,000 to 65,000.

5. １３ 2. The polyolefin wax according to claim 1, wherein the stereoregularity index, as measured by CNMR, is greater than 90%.

6. the content ratio of the structural units derived from propylene is 70 mol% to 88 mol%, 2. The polyolefin wax according to claim 1, wherein the content of the structural units derived from 1-butene is 12 mol % to 30 mol %.

7. 2. The polyolefin wax according to claim 1, wherein the half-width of the crystalline melting point peak measured by a differential scanning calorimeter is 1.0°C to 20.0°C.

8. A resin composition comprising the polyolefin wax according to any one of claims 1 to 7.

9. A coating agent comprising the polyolefin wax according to any one of claims 1 to 7.

10. An adhesive comprising the polyolefin wax according to any one of claims 1 to 7.

Images