Method for producing olefin polymer composition containing structural units derived from organic acid compound

Abstract

SOLUTION: To provide a method for producing an olefin polymer composition which brings an olefin polymer (A), an organic acid compound (B) and a radical initiator (C) into contact with each other in a reactor in a flow condition under the following conditions (X1) to (X3): (X1) condition of Expression (1): 0.01<(Aw(2 / 3) / (Bw×VA(1 / 4)))<100 is satisfied, wherein Aw represents a product (g / cm2 hour) of a percentage content (g / cm3) per volume of the olefin polymer (A) in the flow condition and flow linear velocity (cm / hour) of (A), Bw represents single speed (g / cm2 hour) of (B), and Va is a volume of liquid containing (A) (m3); (X2) temperatures (T)(°C) of (A), (B) and (C) and a 1.5 hr half-life temperature (T1)(°C) of (C) satisfy Expression (2): T1<T<(T1+60); and (X3) contact time of (A), (B) and (C) is 1-20 hours.EFFECT: An olefin polymer composition having desired composition distribution can be obtained, and the composition can be stably produced.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for producing an olefin polymer composition containing structural units derived from an organic acid compound. More specifically, the present invention relates to a method for producing an olefin polymer composition containing structural units derived from an organic acid compound by reacting an organic peroxide, an organic acid compound, and an olefin polymer. [Background technology]

[0002] In the casting of non-ferrous metals such as aluminum, magnesium, and zinc, the die casting method is used, in which a bath of molten non-ferrous metal is poured into a mold at high speed and pressure to form the shape. The die casting method has the advantage of being able to produce products with complex shapes with high precision and efficiency, but it has the problem that the casting surface can be damaged by seizure on the mold. For this reason, mold release agents are used to prevent seizure.

[0003] Conventionally, release agents for die casting have often been made of emulsified mixtures obtained by dispersing the main components, such as mineral oil, vegetable oil, other fats and oils, wax, etc., in water. However, it is known that such water-based release agents do not have sufficient adhesion to high-temperature dies, the amount of components that function effectively is small, and most of them are lost by dispersing into the air as mist, etc.

[0004] In order to improve adhesion efficiency, the use of wax mainly made of polyethylene with a relatively high average molecular weight has been investigated (Patent Document 1). However, wax mainly made of polyethylene is prone to produce by-products of oxidation degradation products with a relatively high molecular weight, which may accumulate on the mold surface, causing changes in the product appearance and a decrease in dimensional accuracy. In addition, polyethylene wax is solid and is said to have a tendency to be difficult to disperse finely in water.

[0005] On the other hand, studies have been conducted on waxes mainly made of polypropylene (Patent Document 2). The wax is prone to molecular chain scission, and the molecular weight of the deteriorated products tends to be low, so the adhesion of oxidized deteriorated products to the mold surface tends to be reduced. In addition, it is said that the dispersibility of polypropylene in water tends to be unfavorable, similar to that of the polyethylene wax. The present applicant has reported that ethylene / α-olefin copolymers and acid-modified products thereof, which have low crystallinity and tend to exhibit fluidity even at room temperature, are suitable for the above-mentioned applications (Patent Document 3). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 61-103642 [Patent Document 2] Japanese Patent Application Publication No. 6-240286 [Patent Document 3] JP 2016-102157 A Summary of the Invention [Problem to be solved by the invention]

[0007] According to the study by the present inventors, it was found that the acid-modified ethylene / α-olefin copolymer disclosed in the above Patent Document 3 may have different performances when used as an aqueous release agent, even if the content of groups derived from organic acid compounds such as maleic anhydride is the same. Furthermore, according to the study by the present inventors, it was found that the viscosity of the aqueous dispersion using the modified ethylene / α-olefin copolymer and the size of the dispersed particles derived from the ethylene / α-olefin copolymer may differ, that the organic acid-modified ethylene / α-olefin copolymer is a composition of a polymer containing a group derived from an organic acid compound, i.e., an organic acid group, and a polymer not containing the group, and that the ratio of the two types of polymers changes due to differences in the shape and size of the production equipment and slight differences in reaction conditions, that is, the composition distribution is easily changed. In addition, the present inventors also found that the viscosity and dispersed particle size of the aqueous dispersion change due to the composition distribution.

[0008] Therefore, the present invention has been made to solve the above problems, that is, the problem to be solved by the present invention is to provide a method capable of controlling an olefin polymer composition containing structural units derived from an organic acid compound having a desired composition distribution, and capable of stably producing such an olefin polymer composition. [Means for solving the problem]

[0009] The present inventors have found that, as long as the range of parameter values ​​determined by a specific formula for some of the requirements for the production conditions in which an olefin polymer is contacted with an organic acid compound and an organic peroxide is within a specific range, an olefin polymer composition having a specific composition can be arbitrarily and stably produced depending on the value, and as a result, olefin polymer compositions containing organic acid-derived groups with different composition distributions can be produced selectively, and thus the present invention has been completed. The present invention is specified by the following requirements.

[0010] [1] A method for producing an olefin polymer composition (AM) containing structural units derived from an organic acid compound (B), comprising contacting an olefin polymer (A), an organic acid compound (B), and a radical initiator (C) in a reactor in a flowing state under conditions that satisfy the following requirements (X1) to (X3): (X1) The fluidized state satisfies the condition represented by the following formula (1). 0.01 < (Aw (2 / 3) / (Bw × VA (1 / 4) )) < 100 …(1) Where Aw, Bw and VA are defined as follows: Aw: Content per volume of the olefin polymer (A) in a fluid state (g / cm 3 ) and the flow linear velocity (cm / hour) of the olefin polymer (A) in a fluidized state (g / cm 2 ·time) Bw: Supply rate per unit area of ​​organic acid compound (B) (g / cm 2 ·time) VA: Volume (m 2 ) of the liquid containing the olefin polymer (A) in a fluidized state present in the reactor. 3 ) (X2) The temperature (T) (°C) when the olefin polymer (A), the organic acid compound (B), and the radical initiator (C) are contacted and the 1.5-hour half-life temperature (T1) (°C) of the radical initiator (C) satisfy the relationship represented by the following formula (2). T1 <T <(T1+60) …(2) (X3) The time period for which the olefin polymer (A), the organic acid compound (B) and the radical initiator (C) are contacted is within the range of 1 to 20 hours.

[0011] [2] The method for producing the olefin polymer composition (AM) according to [1], wherein the olefin polymer (A) satisfies the following requirements (A1) and (A2): (A1) Contains structural units derived from ethylene and structural units derived from an α-olefin having 3 or more carbon atoms, and the content of the ethylene-derived structural units is 10 to 85 mol % (wherein the total of the ethylene-derived structural units and the α-olefin-derived structural units is 100 mol %). (A2) The weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) measurement is 1,000 to 50,000, and the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn value) is 2.5 or less.

[0012] [3] The olefin polymer composition according to [1], which further satisfies the following requirement (X4): Growth A method for manufacturing an object (AM). (X4) The fluidized state satisfies the condition represented by the following formula (3). 0.1<(Aw (2 / 3) / (Cw×VA (1 / 4) ))<1000 …(3) Cw: Supply rate per unit area of ​​radical initiator (C) (g / cm 2 ·time)

[0013] [4] The olefin polymer composition The method for producing an olefin polymer composition (AM) according to [1], wherein (AM) satisfies the following requirements (M1) and (M2): (M1) The mass content (M) of the structural unit derived from an organic acid compound in the olefin polymer composition (AM) is 0.2 to 22 mass% (wherein the olefin polymer composition (AM) is taken as 100 mass%). (M2) The content (MD) of the unreacted olefin polymer (AR) contained in the olefin polymer composition (AM) and the mass content (M) of the structural unit derived from the organic acid compound satisfy the relationship represented by the following formula (4). -4.0×(M)+90 ≧ (MD)≧ -4.0×(M)+60 …(4)

[0014] [5] The method for producing an olefin polymer composition (AM) according to [1], wherein the organic acid compound (B) is a compound (B1) selected from unsaturated carboxylic acids or acid anhydrides thereof.

[0015] [6] The method for producing an olefin polymer composition (AM) according to [1], wherein the organic acid compound (B) is maleic acid and / or maleic anhydride. Effect of the Invention

[0016] The method for producing an olefin polymer composition containing a structural unit derived from an organic acid compound of the present invention can control the composition distribution of the olefin polymer composition to be obtained and can stably produce the olefin polymer composition. In other words, it is possible to produce olefin polymer compositions having various composition distributions. That is, even if the content of the structural unit derived from the same organic acid compound is the same, it is possible to easily select conditions for producing a composition having a high content of the olefin polymer containing the group or a composition having a low content of the same structural unit.

[0017] Therefore, organic solvents that are raw materials for aqueous dispersion compositions with various viscosities and dispersed particle sizes can be used. acid It is possible to provide an olefin polymer containing a group derived from a compound. [Brief description of the drawings]

[0018] [Figure 1] FIG. 1 is a graph showing the relationship between the parameter (Aw(2 / 3) / (Bw×VA(1 / 4))) and the unreacted olefin polymer content (MD) in the examples. [Diagram 2] FIG. 2 is a graph showing the relationship between the parameter (Aw(2 / 3) / (Cw×VA(1 / 4))) and the unreacted olefin polymer content (MD) in the examples. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] The process for producing the olefin polymer composition (AM) of the present invention will be described below. The method for producing the olefin polymer composition (AM) of the present invention is as follows: Weight The method is characterized in that a polymer (A), an organic acid compound (B), and a radical initiator (C) are contacted under specific conditions. The above components may be referred to as component (A), component (B), and component (C), respectively.

[0020] First, the above components (A) to (C) will be described. [Olefi Weight Fusion (A) The olefin polymer (A) according to the present invention can employ any known olefin polymer without any restrictions. For example, olefin homopolymers such as ethylene polymers, propylene polymers, and butene polymers, and olefin copolymers obtained by copolymerizing a plurality of olefins, can be mentioned. The olefin polymer (A) used in the present invention is used in the reaction in a liquid state as described later, and is preferably easily soluble in liquid hydrocarbons such as hexane, heptane, octane, and decane. For this reason, it is preferable that the weight average molecular weight is 500,000 or less. Alternatively, the intrinsic viscosity [η] is preferably 5 dl / g or less, more preferably 3 dl / g or less. On the other hand, the lower limit of the intrinsic viscosity [η] is preferably 0.01 dl / g, more preferably 0.05 dl / g.

[0021] A preferred embodiment of the olefin polymer (A) used in the present invention is an ethylene-based polymer, which more preferably satisfies the following requirements (A1) and (A2).

[0022] (A1) Contains structural units derived from ethylene and structural units derived from an α-olefin having 3 or more carbon atoms, and the content of the structural units derived from ethylene is 10 to 85 mol % (wherein the total of the structural units derived from ethylene and the structural units derived from the α-olefin is 100 mol %).

[0023] The lower limit of the content range of the ethylene-derived structural units in component (A) is preferably 20 mol%, more preferably 30 mol%, even more preferably 40 mol%, and particularly preferably 45 mol%, while the upper limit is preferably 75 mol%, more preferably 70 mol%, and even more preferably 65 mol%.

[0024] If the content is outside the above range, the polymer becomes more likely to crystallize, and as a result, the viscosity of the polymer increases or the polymer becomes solid, which may result in a decrease in dispersibility in water when the polymer is made into an olefin polymer composition described below or an accumulation of oxidized deterioration products when the polymer is used as a release agent.

[0025] The content of ethylene-derived structural units in component (A) was determined according to the method described in "Polymer Analysis Handbook" (Asakura Publishing, 2008, first edition, pp. 184-211). 13 It is measured by C-NMR. In addition, if a calibration curve is prepared based on the absorption intensity ratio of a specific peak in an IR spectrum using Fourier transform infrared spectroscopy (FT-IR) or the like, using a sample determined by this method as a known sample, it is also possible to specify the content of ethylene-derived structural units using the IR method. The content is a value when the total content of structural units derived from all olefins is taken as 100 mol %.

[0026] (A2) The weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) measurement is 1,000 to 50,000, and the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn value, molecular weight distribution) is 2.5 or less.

[0027] The weight average molecular weight (Mw) of component (A) is a value obtained by measuring by gel permeation chromatography (GPC) according to the method described later and converting it into standard polystyrene. The weight average molecular weight (Mw) of component (A) is 1,000 to 50,000, preferably 1,500 to 30,000, more preferably 1,500 to 20,000, and particularly preferably 1,500 to 7,000. If Mw is excessively below the above range, the amount of easily volatile components is high, making it easy to ignite and causing deterioration in storage stability, or the evaporation loss in the aqueous dispersion increases, or when used as a die-casting release agent, the amount of adhesion to the die decreases, causing deterioration in release performance. In addition, if Mw is excessively above the above range, the viscosity of the polymer increases, and it may become difficult to disperse uniformly in water.

[0028] The Mw / Mn value of component (A) is measured by gel permeation chromatography (GPC) according to the method described below, and is calculated as the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by standard polystyrene conversion. The Mw / Mn value of component (A) is 2.5 or less, preferably 2.3 or less, and more preferably 2.0 or less. The Mw / Mn value exceeding the above range means that the polymer contains a large amount of low molecular weight components and high molecular weight components. When the polymer contains a large amount of low molecular weight components, the polymer may be easily flammable due to the large amount of easily volatile components, resulting in poor storage stability or an increase in evaporation loss in the aqueous dispersion. When the polymer contains a large amount of high molecular weight components, the viscosity of the copolymer increases, and it may become difficult to disperse uniformly in water.

[0029] In some cases, it may be preferable that the olefin polymer (A) used in the present invention satisfies the following requirements (A3) to (A6) in addition to the above requirements.

[0030] (A3) Kinematic viscosity at 100°C is 10 to 5,000 mm 2 / s. The kinetic viscosity of component (A) is a value measured by the method described in JIS K2283. The kinetic viscosity of component (A) at 100°C is 10 to 5,000 mm 2 / s, preferably 10 to 2,500 mm 2 / s, more preferably 15 to 2,500 mm 2 / s, particularly preferably 15 to 500 mm 2 / s. If the kinetic viscosity is too low, the amount of volatile components is high, which makes the polymer more flammable and reduces storage stability, the evaporation loss in the aqueous dispersion increases, and the amount of high molecular weight components that easily adhere to the die when used as a die-casting release agent decreases. If the kinetic viscosity is too high, the viscosity of the polymer increases, making it difficult to disperse the polymer uniformly in water.

[0031] (A4) When the olefin polymer (A) is a copolymer, it has a B value defined by the following formula (5) of 1.1 or more. A more preferable B value is 1.2 or more. There is no particular upper limit to the B value, but it is usually 2.0 or less. B=P O1-O2 / (2×P O1 ×P O2 ) (5)

[0032] In the above formula (5), P O1 represents the molar fraction of the structural unit derived from the first olefin, and P O2 represents the molar fraction of the structural unit derived from the second olefin, and P O1-O2 indicates the mole fraction of the "first olefin-second olefin" chain in all dyad chains. In the present invention, either the first olefin or the second olefin is ethylene.

[0033] The B value is an index showing the randomness of the distribution of copolymerized monomer sequences in a copolymer, and is expressed by P in the above formula [1]. O1 , P O2 , P O1-O2 teeth, 13 The C-NMR spectrum can be measured and the value can be determined based on known literature such as the reports of JC Randal [Macromolecules, 15, 353 (1982)] and J. Ray [Macromolecules, 10, 773 (1977)], "Polymer Analysis Handbook" (Asakura Publishing, first edition, published in 2008, pp. 184-211).

[0034] The larger the B value, the fewer the chain structures of ethylene-derived structural units and α-olefin-derived structural units, the more uniform the distribution of ethylene-derived structural units and α-olefin-derived structural units, and the narrower the composition distribution of the copolymer. As a result, the larger the B value, the less likely component (A) will crystallize, and the less likely component (A) will increase in viscosity or become solid, and the less likely its dispersibility in water will deteriorate. Specific conditions for measuring the B value are as described in the Examples.

[0035] (A5) 1 The amount of unsaturated bonds measured by H-NMR is less than 0.5 per 1,000 carbon atoms. The molecule of component (A) has 1 The total number of double bonds derived from vinyl, vinylidene, disubstituted olefins, trisubstituted olefins, etc. (hereinafter also referred to as "unsaturated bond amount") measured by H-NMR is less than 0.5, preferably less than 0.3, more preferably less than 0.2, and particularly preferably less than 0.1 per 1000 carbon atoms. When the unsaturated bond amount is within this range, the heat resistance of component (A) is good. The specific measurement conditions for the unsaturated bond amount are as described in the examples.

[0036] (A6) No melting point is observed. It is preferable that component (A) has no observed melting point in differential scanning calorimetry (DSC). Here, "no observed melting point (Tm)" means that the heat of fusion (ΔH) (unit: J / g) measured by differential scanning calorimetry (DSC) is not substantially measured. "No substantially measured heat of fusion (ΔH)" means that no peak is observed in differential scanning calorimetry (DSC) or the observed heat of fusion is 1 J / g or less.

[0037] The melting point (Tm) and heat of fusion (ΔH) of component (A) are determined by performing differential scanning calorimetry (DSC) and analyzing the DSC curve with reference to JIS K7121 when the component is cooled to -100°C and then heated to 150°C at a heating rate of 10°C / min. If no melting point is observed, this means that component (A) has low crystallinity, does not increase in viscosity, does not become solid, and has excellent dispersibility in water.

[0038] Examples of the olefin derived from the constituent units of component (A) include ethylene and α-olefins having 3 or more carbon atoms. Specific examples of the α-olefins include linear or branched α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

[0039] The α-olefin is preferably a linear or branched α-olefin having 3 to 10 carbon atoms, more preferably at least one selected from propylene, 1-butene, 1-hexene, and 1-octene, and most preferably propylene in terms of the fluidity of an aqueous dispersion composition using the resulting olefin polymer composition.

[0040] The α-olefins can be used alone or in combination of two or more. In addition, the component (A) can be obtained by using an addition polymerizable compound selected from a polar group-containing vinyl compound, an aromatic vinyl compound, an alicyclic vinyl compound, and a cyclic olefin together with the α-olefin. The addition polymerizable compound can be used in an amount of, for example, 20 parts by mass or less, preferably 10 parts by mass or less, based on 100 parts by mass of the total of ethylene and α-olefin.

[0041] Examples of the polar group-containing vinyl compound include α,β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, and maleic anhydride, and metal salts thereof such as sodium salts, α,β-unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, methyl methacrylate, and ethyl methacrylate, vinyl esters such as vinyl acetate and vinyl propionate, and unsaturated glycidyls such as glycidyl acrylate and glycidyl methacrylate.

[0042] Examples of aromatic vinyl compounds include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, methoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, p-chlorostyrene, divinylbenzene, α-methylstyrene, and allylbenzene.

[0043] An example of the alicyclic vinyl compound is vinylcyclohexane. Examples of the cyclic olefin include cyclic olefins having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, and tetracyclododecene.

[0044] The component (A) may be used alone or in combination of two or more kinds. For example, two or more kinds of components (A) having different molecular weights, two or more kinds having different monomer compositions, or two or more kinds of components (A) having different molecular weights and monomer compositions may be used in combination.

[0045] The method for producing component (A) is not particularly limited, but includes a method using a vanadium catalyst containing a vanadium compound and an organoaluminum compound as described in JP-B-2-1163 and JP-B-2-7998. In addition, as a method for producing a copolymer with high polymerization activity, a method using a metallocene catalyst containing a metallocene compound (e.g., zirconocene) and an organoaluminum oxy compound (e.g., aluminoxane) as described in JP-A-61-221207, JP-B-7-121969, Japanese Patent No. 2796376, and Japanese Patent No. 4367687 may be used, and the method using a metallocene catalyst is more preferred because it can reduce the chlorine content of the resulting copolymer and the 2,1-insertion amount of propylene.

[0046] In the process using a vanadium catalyst, a larger amount of a chlorine compound is used as a co-catalyst compared to the process using a metallocene catalyst, so there is a possibility that a small amount of chlorine will remain in the obtained component (A).

[0047] On the other hand, in the method using a metallocene catalyst, the catalyst has an extremely low content of halogens such as chlorine, and in some cases can be made halogen-free, so that the halogen content of the obtained olefin polymer (A) can be made extremely low. Therefore, when the olefin polymer composition (AM) is used to prepare an aqueous dispersion as described below, the possibility of promoting corrosion of metal parts of the storage container, etc. can be significantly reduced.

[0048] The chlorine content in the component (A) is preferably 100wtppm or less, more preferably 50wtppm or less, even more preferably 20wtppm or less, and particularly preferably 5wtppm or less. The chlorine content can be quantified by a known method such as an ICP method.

[0049] In addition, in the component (A), 2,1 addition may occur in the chain of propylene units. A reduction in the content of structural units derived from such 2-1 addition (hereinafter, sometimes referred to as 2,1-insertion amount) makes it possible to further reduce the ethylene chains in the copolymer molecule, and since the intramolecular crystallinity of ethylene can be suppressed, such a copolymer tends to have excellent dispersibility in water. The 2,1-insertion amount of propylene can be reduced according to the method described in JP-A-7-145212. 13 It is determined by C-NMR measurement analysis, and is preferably less than 1%, more preferably 0 to 0.5%, and even more preferably 0 to 0.1%. It is particularly preferable that no peak is observed in the range of 15.0 to 17.5 ppm. Such a component (A) is often obtained using a metallocene catalyst.

[0050] When the above-mentioned metallocene compound is used, a component (A) having a good balance of performance in terms of molecular weight control, molecular weight distribution, amorphousness, and B value can often be obtained. As such a metallocene compound, for example, a metallocene compound disclosed in JP 2019-021576 A can be mentioned as a preferred example. One of the preferred methods for obtaining component (A) is to polymerize the above-mentioned ethylene, α-olefin, etc. using an olefin polymerization catalyst containing such a metallocene compound and a component selected from an organoaluminum oxy compound, a compound that reacts with the metallocene compound to form an ion pair, and an organometallic compound.

[0051] The kinetic viscosity at 100°C of the olefin polymer (A) used in the present invention depends on its molecular weight. That is, the kinetic viscosity at 100°C is adjusted by adjusting the molecular weight of the component (A). In addition, by removing low molecular weight components from the polymer obtained by a conventionally known method such as vacuum distillation, the molecular weight distribution (the Mw / Mn value is an index thereof) of the obtained polymer can be narrowed and adjusted. Furthermore, the olefin polymer obtained by the above-mentioned method may contain double bonds. In such a case, hydrogenation (hereinafter also referred to as "hydrogenation") may be performed by a known method as necessary. The amount of unsaturated bonds in the polymer obtained by hydrogenation can be reduced. Such an olefin polymer tends to have improved oxidation stability and heat resistance.

[0052] The olefin polymer (A) used in the present invention is used in a liquid state. The liquid olefin polymer can be used as it is. On the other hand, the solid olefin polymer can be used in a liquid state by dissolving it in a known hydrocarbon solvent. Preferred examples of the hydrocarbon solvent include butane, pentane, hexane, heptane, octane, decane, dodecane, tetradecane, hexadecane, octadecane, and other hydrocarbon compounds that become liquid under normal pressure conditions or under pressurized conditions.

[0053] The so-called polymer concentration (mass of the olefin polymer (A) per unit volume) of the solution of the olefin polymer (A) dissolved in the above-mentioned solvent is 0.001 to 0.9 g / cm 3 A more preferable lower limit is 0.005 g / cm 3 , and more preferably 0.01 g / cm 3 On the other hand, a more preferable upper limit is 0.85 g / cm 3 , and more preferably 0.85 g / cm 3 , particularly preferably 0.83 g / cm 3 It is.

[0054] When the olefin polymer (A) itself is in a liquid state, it can be used as it is. In this case, the above-mentioned polymer concentration corresponds to the density of the olefin polymer (A) itself. As is apparent from the above, the olefin polymer (A) in a liquid state in the present invention refers to an embodiment containing all components constituting a liquid state, such as the olefin polymer (A) and the hydrocarbon solvent.

[0055] [Organic acid compound (B)] An organic acid compound (B) is used in the production of the olefin polymer composition (AM) of the present invention described later. As such a compound, any organic acid compound known as a raw material for the graft reaction of so-called olefin polymers can be used without limitation. As the organic acid compound (B), mainly, unsaturated carboxylic acids having 3 to 10 carbon atoms, preferably 3 to 8 carbon atoms, and derivatives of the unsaturated carboxylic acids can be mentioned. As derivatives of unsaturated carboxylic acids, for example, acid anhydrides, esters, amides, and imides of unsaturated carboxylic acids can be mentioned. Among them, unsaturated carboxylic acids, their ester compounds, amide compounds, imide compounds, and the like are preferred examples.

[0056] Specific examples of such unsaturated carboxylic acids include monobasic acids such as acrylic acid and methacrylic acid; and dibasic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, and 5-norbornene-2,3-dicarboxylic acid.

[0057] Examples of the acid anhydrides of unsaturated carboxylic acids include acid anhydrides of dibasic acids such as maleic acid, itaconic acid, citraconic acid, and 5-norbornene-2,3-dicarboxylic acid.

[0058] Examples of the esters of unsaturated carboxylic acids include esters and half esters such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, glycidyl acrylate, monoethyl maleate, diethyl maleate, monomethyl fumarate, dimethyl fumarate, monomethyl itaconic acid, and diethyl itaconic acid.

[0059] Examples of the amide of the unsaturated carboxylic acid include acrylamide, methacrylamide, maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, maleic acid-N,N-diethylamide, maleic acid-N-monobutylamide, maleic acid-N,N-dibutylamide, fumaric acid monoamide, fumaric acid diamide, fumaric acid-N-monobutylamide, and fumaric acid-N,N-dibutylamide. Examples of the imide of the unsaturated carboxylic acid include maleimide, N-butylmaleimide, and N-phenylmaleimide.

[0060] Among these, maleic acid, maleic anhydride, and maleic acid (half) ester are preferred because they are highly polar and are less likely to produce by-products such as homopolymers in a modification reaction using a peroxide. Maleic anhydride is particularly preferred. These organic acid compounds (B) can also be used in combination of two or more kinds. When two or more kinds are used in combination, it is preferred that they contain at least one selected from the above-mentioned maleic acid, maleic anhydride, and maleic anhydride (half). The most preferred embodiment is one that contains maleic anhydride.

[0061] [Radical initiator (C)] The radical initiator (C) used in the present invention may be a known compound such as an organic peroxide or an azo compound that is used as an initiator for radical polymerization or graft reaction. Organic peroxides are preferred. Organic peroxides are preferred compounds because many different types of compounds with different half-lives are commercially available.

[0062] Specific examples of organic peroxides include dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, 1,3-bis(t-butylperoxyisopropyl)benzene, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(t-butylperoxy)valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butyl peroxybenzoate, t-butyl perbenzoate, t-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and t-butylcumyl peroxide.

[0063] Examples of the azo compound include 2,2"-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2"-azobis(2-methylbutylnitrile), 2,2"-azobis(isobutyronitrile), and dimethyl 2,2"-azobis(2-methylpropionate).

[0064] In consideration of the industrially preferred reaction temperature using an olefin polymer, the radical initiator (C) of the present invention has a 1.5-hour half-life temperature in the range of, for example, 50°C to 250°C. The lower limit of the 1.5-hour half-life temperature range is more preferably 70°C, even more preferably 80°C, and particularly preferably 90°C. On the other hand, the upper limit is more preferably 230°C, even more preferably 210°C, and particularly preferably 200°C. In addition, in the case of the 10.5-hour half-life temperature, the range specified by the upper and lower limits 20°C higher than the above 1.5-hour half-life temperature is preferable. As an example, the 1.5-hour half-life temperature of di-t-butyl peroxide used in the examples of the present invention is 144.1°C, and the 10.5-hour half-life temperature is 123.7°C. These radical initiators (C) may be used alone or in combination of two or more.

[0065] [Method for producing olefin copolymer composition (AM)] The method for producing an olefin polymer composition (AM) containing structural units derived from an organic acid compound (B) of the present invention can be carried out, for example, by contacting an olefin polymer (A), an organic acid compound (B) and a radical initiator (C) in a flowing state in a reactor. The present invention is characterized in that the following requirements (X1), (X2) and (X3) are satisfied during this contact. (X1) The fluidized state satisfies the condition represented by the following formula (1). 0.01 < (Aw (2 / 3) / (Bw × VA (1 / 4) )) < 100 (1) However, Aw, Bw, and VA are defined as follows: Aw: Content per volume of the olefin polymer (A) in a fluid state (g / cm 3 ) and the flow linear velocity (cm / hour) of the olefin polymer (A) in a fluidized state (g / cm 2 ·time) Bw: Supply rate per unit area of ​​organic acid compound (B) (g / cm 2 ·time) VA: Volume (m 2 ) of the liquid containing the olefin polymer (A) in a fluidized state present in the reactor. 3 ) (X2) The temperature (T) (°C) when the olefin polymer (A), the organic acid compound (B), and the radical initiator (C) are contacted and the 1.5-hour half-life temperature (T1) (°C) of the radical initiator (C) satisfy the relationship represented by the following formula (2). T1 <T <(T1+60) (2) (X3) The time period for which the olefin polymer (A), the organic acid compound (B) and the radical initiator (C) are contacted is within the range of 1 to 20 hours.

[0066] A method for producing an olefin polymer containing a structural unit derived from an organic acid compound (B) by contacting an olefin polymer (A), an organic acid compound (B), and a radical initiator (C) is known. It is also known that an olefin polymer not containing a structural unit derived from an organic acid compound (B) (hereinafter, sometimes referred to as an unreacted olefin polymer) remains in the reaction product obtained by this method. Therefore, it can be said that the product obtained by the above-mentioned production method is an olefin polymer composition.

[0067] According to the study by the present inventors, it has been found that even if the content of structural units derived from the organic acid compound (B) is the same, the content of unreacted olefin polymer may differ depending on the conditions of the above-mentioned production method. It has also been found that the dispersion particle size and viscosity of the aqueous dispersion using the olefin polymer composition may differ depending on the balance of the content of the above-mentioned unreacted olefin polymer, as described below. The release agent performance may also differ depending on the balance of these physical properties. Therefore, it can be said that it is important to select production conditions that can produce olefin polymer compositions having different balances between the content of structural units derived from the organic acid compound (B) and the content of unreacted olefin polymer.

[0068] (Production Condition 1 (X1)) As a result of investigations by the present inventors from the above viewpoints, it was found that by using the requirement (X1), it is possible to predict to some extent the balance of the content ratios, including cases where the reaction scale is different.

[0069] The above requirement (X1) is 0.01 < (Aw (2 / 3) / (Bw × VA (1 / 4) )) < 100 and Aw, Bw, and VA are defined as follows: Aw: Content per volume of the olefin polymer (A) in a fluid state (g / cm 3 ) and the flow linear velocity (cm / hour) of the olefin polymer (A) in a fluidized state (g / cm 2 ·time) Bw: Supply rate per unit area of ​​organic acid compound (B) (g / cm 2 ·time) VA: Volume (m 2 ) of the liquid containing the olefin polymer (A) in a fluidized state present in the reactor. 3 )

[0070] The Aw is an index of the supply rate of the olefin polymer (A) to the peripheral area of ​​the contact area of ​​each component during the contact. The Bw is an index of the supply rate of the organic acid compound (B) to the peripheral area of ​​the contact area. For example, when the organic acid compound (B) is supplied from a supply tank to the liquid surface in the reactor or is supplied through a supply line connected to the liquid, the Bw can be calculated as the quotient of the supply rate divided by the area of ​​the line outlet.

[0071] For example, when the olefin polymer (A) is fed dropwise from a feed tank to a reactor, Aw is the product of the dropping rate, i.e., the linear velocity, and the volume density. On the other hand, when the olefin polymer (A) is charged in a reactor all at once, Aw is the product of the stirring linear velocity calculated from the stirring speed and the distance from the center of the stirrer, and the volume density, since the polymer is usually fluidized by stirring or the like.

[0072] The above VA is the volume of a liquid containing the olefin polymer (A), which is the most important component used in the production method of the present invention. More specifically, it is the volume of the liquid olefin polymer (A) supplied into the reactor. If the olefin polymer (A) is liquid, the olefin polymer (A) itself can be used in the form of a block. The olefin polymer (A) can also be used in the form of a liquid by using a known solvent such as a hydrocarbon solvent in combination. In this case, VA refers to the volume including the hydrocarbon solvent. There is no particular limit to the value of VA, but if it is too high or too low, it may not be practical. A preferred numerical range for VA is 10 -5 ~10000m 3 , more preferably 3×10 -5 ~7000m 3 , and more preferably 3 × 10 -5 ~7000m 3 It is.

[0073] The production method of the present invention can use a semi-batch reaction method or a continuous reaction method. The continuous reaction method is a method in which the reaction is carried out while a part of the reaction solution is withdrawn. In this case, the VA is defined as the difference between the liquid olefin polymer (A) fed into the reactor and the liquid olefin polymer (A) corresponding to the amount withdrawn from the reactor during the withdrawal operation. The volume of the liquid olefin polymer (A) corresponding to the amount withdrawn can be calculated by a conventional method from the continuous reaction conditions.

[0074] Usually, when the above-mentioned components (A), (B) and (C) are brought into contact with each other and made to coexist, if the composition is always uniform throughout the reaction system, it is considered that, in principle, the balance between the content of the structural unit derived from the organic acid compound (B) and the content of the unreacted olefin polymer will not change. On the other hand, in the production method of the present invention, the ratio of the above-mentioned component (A) is often higher than the other two components, and in such a case, a method of feeding the components (B) and (C) to the reaction system after feeding the component (A) into the reactor is one of the preferred embodiments. In such a case, when feeding the components (B) and (C), the local compositions of the components (A), (B) and (C) near the feeding location tend to be different from the overall compositions of the components (A), (B) and (C). In particular, the larger the scale, the relatively lower the diffusion speed of each component, so that the above-mentioned composition difference will tend to occur more easily. In other words, there is likely to be a time lag until the supplied components are sufficiently diffused and homogenized. Under conditions that tend to cause this kind of non-uniformity, the ratio of the unreacted olefin polymer will tend to increase. On the other hand, under conditions that tend to make the mixture homogenous virtually instantaneously, the ratio of the unreacted olefin polymer will tend to decrease.

[0075] From the above viewpoint, it is considered that the likelihood of the non-uniformity occurring is mainly governed by the feed rates of components (A), (B), and (C), and the scale of the entire reaction system. It is expected to be particularly susceptible to the balance between the feed rates of components (A) and (B), which are used at a high ratio, and the scale of the reaction system.

[0076] As a result of investigations including the above-mentioned ideas, the present inventors concluded that (2 / 3) / (Bw × VA (1 / 4) It has been found that an index specified by the parameter formula "(Aw ))" is useful, for example, as an index for predicting the progress of the content of unreacted olefin polymer when the content of structural units derived from the organic acid compound (B) is constant. For example, those skilled in the art will understand that if Aw is large and Bw is low, homogenization by diffusion will be more likely to occur. Furthermore, those skilled in the art will understand that the smaller the scale, the more likely homogenization by diffusion will be. That is, "(Aw (2 / 3) / (Bw × VA (1 / 4) ))" indicates that, when the value is large, homogenization by diffusion is likely to occur and the content of unreacted olefin polymer is likely to be low, and conversely, when the value is small, it can be considered to be an index that homogenization by diffusion takes time and the content of unreacted olefin polymer is likely to be high.

[0077] As disclosed in the examples below, the present invention (2 / 3) / (Bw × VA (1 / 4) Since the index "(%)" tends to be less affected by the reaction scale, it can be suitably used for selecting conditions, including control of the unreacted olefin polymer ratio, when scaling up the results of a small-scale test.

[0078] Of course, the above index is not an index for determining the absolute value of the content of unreacted olefin polymer, but can be used as an index for selecting the production conditions of an olefin polymer composition having a desired content of unreacted olefin polymer, regardless of the reaction scale, in a composition having a specific content of structural units derived from the organic acid compound (B) contained in the olefin polymer composition (AM).

[0079] For this reason, one of the advantages of the index of the present invention is that the results of laboratory-scale experiments can be used for bench-scale or medium-scale tests, and even for selecting conditions for implementing the experiment using (existing) equipment on a commercial scale. In addition, the index will be useful when designing a commercial scale manufacturing equipment based on the results of laboratory scale experiments.

[0080] The above "(Aw (2 / 3) / (Bw × VA (1 / 4) The lower limit of "(x))" is preferably 0.1, more preferably 0.3, and even more preferably 0.5. On the other hand, the upper limit is preferably 90, and more preferably 80. If it is outside the above range, the change in the unreacted olefin polymer due to the difference in the index value becomes small, and the index may not be suitable as an index.

[0081] The above index depends on the content of structural units derived from the organic acid compound (B) contained in the olefin polymer composition (AM), but when the index value exceeds approximately 5, the composition has a relatively low content of unreacted olefin polymer, and when the index value is 5 or less, the composition has a relatively high content of unreacted olefin polymer.

[0082] In the present invention, in addition to the above, the supply rate of the radical initiator (C) is also taken into consideration. (2 / 3) / (Cw × VA (1 / 4) Here, Cw is the supply rate per unit area of ​​the radical initiator (C) per hour (g / cm 2 The calculation method for Cw is basically the same as that for Bw.

[0083] Aw and VA are the same as above. This index is also specified for the same reason as above. Its lower limit is preferably 0.1, more preferably 0.3, and even more preferably 0.5. On the other hand, its upper limit is preferably 1000, more preferably 900, and even more preferably 800. The larger the value of this index, the more likely it is that homogenization by diffusion occurs, and an olefin polymer composition (AM) having a low content of unreacted olefin polymer is likely to be generated, and the smaller the value, the more likely it is that an olefin polymer composition (AM) having a high content of unreacted olefin polymer is likely to be obtained.

[0084] The above index depends on the content of structural units derived from the organic acid compound (B) contained in the olefin polymer composition (AM), but when the index value exceeds approximately 25, the composition has a relatively low content of unreacted olefin polymer, and when the index value is 25 or less, a composition with a relatively low content of unreacted olefin polymer tends to be obtained.

[0085] The organic acid compound (B) of the present invention is preferably used in a ratio of 0.1 to 30 parts by mass based on 100 parts by mass of the olefin polymer (A). A more preferred lower limit is 0.5 parts by mass, and even more preferred is 1 part by mass. On the other hand, a more preferred upper limit is 25 parts by mass, and even more preferred is 22 parts by mass, and particularly preferred is 20 parts by mass. The radical initiator (C) is usually used in an amount of 0.01 to 30 parts by mass based on 100 parts by mass of the olefin polymer (A).

[0086] (Production Condition 2 (X2)) The temperature (T) when the olefin polymer (A), the organic acid compound (B), and the radical initiator (C) are contacted and the 1.5-hour half-life temperature (T1) of the radical initiator (C) satisfy the relationship represented by the following formula (2). The unit of the temperature is Celsius. T1 <T <(T1+60) (2) Regarding the range of the difference between T and T1, the lower limit is preferably 5°C, more preferably 10°C, while the upper limit is preferably 50°C, more preferably 45°C.

[0087] It is also preferable that the above temperature (T) and the 10.5-hour half-life temperature (T2) of the radical initiator (C) satisfy the relationship represented by the following formula (2). T2+20 <T <(T2+80) Regarding the range of the difference between T and T2, the lower limit is preferably 25°C, more preferably 30°C, while the upper limit is preferably 70°C, more preferably 65°C.

[0088] Within the above temperature range, the reaction between the olefin polymer (A) and the organic acid compound (B) occurs easily, and the olefin polymer composition (AM) of the present invention can be produced efficiently.

[0089] (Manufacturing conditions (X3)) The time for contacting the olefin polymer (A), the organic acid compound (B) and the radical initiator (C) is within the range of 1 to 20 hours, preferably 1.5 to 17 hours, more preferably 2 to 15 hours. Within the above temperature range, the reaction between the olefin polymer (A) and the organic acid compound (B) easily occurs, and the olefin polymer composition (AM) of the present invention can be efficiently produced.

[0090] The contacting operation of the above-mentioned components can be, for example, a method similar to the so-called grafting reaction described in JP-A-61-126120. More specifically, for example, 1. A method in which an organic acid compound (B) is gradually added to an olefin polymer (A) in the presence of a radical initiator such as di-t-butyl peroxide can be mentioned. 2. There is also a method in which an organic acid compound (B) and a radical initiator (C) are gradually added to an olefin polymer (A). 3. There is also a method in which the radical initiator (C) is gradually added to the olefin polymer (A) in the presence of the organic acid compound (B).

[0091] In the case of large-scale production, in consideration of the high reactivity of the radical initiator, the above methods 2 and 3 are more preferable, and the above method 3 is particularly preferable. In the contact step, it is preferable that the components (A), (B), and (C) are all used in liquid form. If they are in liquid form, a rapid and uniform reaction tends to occur when the components are contacted. When the components (A), (B), and (C) are solid, they can be liquefied using a liquid hydrocarbon compound as a solvent. In this case, the concentrations of the components (A) to (C) are preferably 10 to 99% by mass, more preferably 15 to 95% by mass, and even more preferably 20 to 90% by mass. Of course, when the components (A) to (C) are liquid, they may be used as they are. In this case, the above concentrations correspond to 100% by mass.

[0092] Then, the mixture is contacted under conditions that satisfy the above-mentioned requirements to produce an olefin polymer composition (AM). In the method for producing the olefin polymer composition (AM) of the present invention, the above reaction is preferably carried out in a semi-batch or continuous manner using a stirred reactor or a line reactor. The size of such a reactor can be applied from a laboratory scale to a commercial facility. The volume of the reactor is preferably 2×10 -5 ~15000m 3 , more preferably 5 × 10 -5 ~12000m 3 , and more preferably 7 × 10 -5 ~10000m 3 It is. Regarding items other than the above conditions, known methods such as those described in Patent Document 3 can be used without any restrictions.

[0093] (Olefin polymer composition (AM)) In the present invention, the olefin polymer composition (AM) is WeightThe olefin polymer composition (AM) is obtained by contacting the polymer (A), an organic acid compound (B), and a radical initiator (C) under specific conditions. More specifically, the olefin polymer composition (AM) is a composition containing a so-called acid-modified product containing structural units derived from the organic acid compound (B) and a so-called unreacted olefin polymer not containing structural units derived from the organic acid compound (B).

[0094] The olefin polymer composition obtained by the process for producing an olefin polymer composition of the present invention preferably satisfies the following requirements (M1) and (M2). (M1) The mass content (M) of the structural unit derived from an organic acid compound in the olefin polymer composition (AM) is 0.2 to 22 mass%. (The olefin polymer composition (AM) is taken as 100 mass%). The lower limit of (M) is preferably 0.5 mass%, more preferably 0.8 mass%, and even more preferably 1 mass%. On the other hand, the upper limit of (M) is preferably 20 mass%, more preferably 18 mass%, and even more preferably 15 mass%. If the value of (M) is too small, the desired modifying effect may not be sufficient. On the other hand, if the value of (M) is too large, the properties derived from the olefin unit chain may not be fully expressed, or the viscosity may become too high during the production of the polymer of the present invention, making it impossible to control the reaction.

[0095] The content of the structural unit derived from these organic acid compounds is determined by the charge ratio when the olefin polymer and the organic acid compound are reacted in the presence of a radical initiator or the like, or, as described above, 13 C NMR measurements and 1 The measurement can be performed by known means such as H NMR measurement. Specific NMR measurement conditions include the following conditions.

[0096] 1 For H NMR measurements, a nuclear magnetic resonance apparatus of the ECX400 model manufactured by JEOL Ltd. was used, the solvent was deuterated orthodichlorobenzene, the sample concentration was 20 mg / 0.6 mL, the measurement temperature was 120 °C, and the observation nucleus was 1The conditions were: H (400 MHz), sequence was single pulse, pulse width was 5.12 μsec (45° pulse), repetition time was 7.0 sec, and the number of integrations was 500 or more. The reference chemical shift was set to 0 ppm for hydrogen in tetramethylsilane, but similar results can be obtained by using, for example, the peak derived from the residual hydrogen in deuterated orthodichlorobenzene as the reference value for the chemical shift at 7.10 ppm. 1 Peaks such as H were assigned by standard methods.

[0097] 13 For C NMR measurements, the measurement equipment was a JEOL ECP500 type nuclear magnetic resonance spectrometer or a Bruker Biospin AVANCEIIIcryo-500 type nuclear magnetic resonance spectrometer, the solvent was a mixed solvent of orthodichlorobenzene / heavy benzene (80 / 20% by volume), the measurement temperature was 120°C, and the observation nuclei were 13 The conditions are: C (125 MHz), single pulse proton decoupling, 45° pulse, repetition time 5.5 seconds, number of integrations 10,000 or more, and chemical shift reference value 27.50 ppm. Assignment of various signals is performed based on the usual method, and quantification can be performed based on the integration value of signal intensity.

[0098] When a clear structural unit having a functional group such as a carboxylic acid, such as maleic anhydride, is contained, it can be quantitatively determined by a titration method such as the saponification value. Alternatively, when the basic structure of the functional group contained is clear, the content of elements derived from the functional group, such as oxygen and nitrogen, can be measured by elemental analysis of the sample, and the functional group content can be calculated by a conventional method.

[0099] Another simple method for measuring the content of functional group structural units is to determine the functional group contents of polymers with different functional group contents by the above-mentioned NMR measurement method, titration method, elemental analysis method, etc., measure these polymers by infrared spectroscopy (IR), create a calibration curve based on the intensity ratio of a specific peak, and determine the functional group content based on this result. Although this method is simpler than the above-mentioned NMR measurement method, it is basically necessary to create a corresponding calibration curve depending on the type of base resin and functional group. For these reasons, this method is preferably used for process management in resin production at a commercial plant, for example. As a specific measurement method by infrared spectroscopy in the present invention, a preferred method will be introduced.

[0100] (Preparation of calibration curve) A plurality of liquid olefin polymers having different maleic anhydride structural unit contents are prepared as standard samples for preparing a calibration curve. 13 This is determined in advance by a method such as C NMR measurement or oxygen content measurement by elemental analysis. These polymers are subjected to infrared spectroscopy measurement by the following method.

[0101] A specific example of an IR measurement device is the FT-IR 4100 infrared spectroscopy device manufactured by JASCO Corporation. The sample was subjected to infrared spectroscopy measurement using the KBr thin film method under room temperature conditions, and the 1682 cm -1 Intensity (D) and 4320cm -1 The absorption intensity (D0) of a specific wavenumber in the vicinity is measured. A two-axis graph is prepared with the maleic anhydride structural unit content and the D / D0 intensity ratio as axes, and this is used as a calibration curve.

[0102] (Determination of Maleic Anhydride Structural Unit Content) The sample to be measured is subjected to infrared spectroscopy in the same manner as above, and the D / D0 intensity ratio is determined. Next, the maleic anhydride structural unit content is determined using the above calibration curve and the D / D0 intensity ratio. (M2) The content (MD) of the unreacted olefin polymer (AR) contained in the olefin polymer composition (AM) and the mass content (M) of the structural unit derived from the organic acid compound satisfy the relationship represented by the following formula (4). -4.0×(M)+90 ≧ (MD) ≧ -4.0×(M)+60 …(4)

[0103] If the olefin polymer composition (AM) satisfies the above range, the viscosity and dispersed particle size of an aqueous dispersion containing the composition can be set within a practical range, and it tends to be relatively easy to control the above physical properties by (M) and (MD).

[0104] The content of the unreacted olefin polymer (AR) can be determined by using column chromatography as described in the examples. As described above, component (A), which is the starting material of the olefin polymer composition (AM), has a small amount of unsaturated bonds, and therefore, it is presumed that the component of the olefin polymer composition (AM) containing structural units derived from the organic acid compound (B) has a structure in which structural units derived from component (B) are randomly bonded to the main chain skeleton of component (A). The olefin polymer composition (AM) preferably satisfies the following (AM1) to (AM5).

[0105] (AM1) Acid value is 1 to 300 mg KOH / g. The acid value is used as an index of the graft amount of the graft component. The acid value of the olefin polymer composition (AM) is preferably 1 to 300 mgKOH / g, more preferably 5 to 200 mgKOH / g, and further preferably 10 to 150 mgKOH / g. If the acid value is below the above range, the polarity of the polymer may be reduced, and the stability of the aqueous dispersion may be reduced. If the acid value is above the above range, hydrogen bonds may be formed between the graft components, and the viscosity of the polymer may increase, resulting in a decrease in dispersibility in water.

[0106] The acid value of the olefin polymer composition (AM) can be adjusted by the value of (M). For example, a method for obtaining an olefin polymer composition (AM) having a high acid value requires a high ratio of the component (B).

[0107] The acid value of the olefin polymer composition (AM) indicates the number of milligrams of potassium hydroxide required to neutralize the acid contained in 1 g of the polymer, and is measured according to the method in accordance with JIS K0070. Specifically, this can be done as described in the Examples.

[0108] (AM2) Apparent viscosity at 150°C is 1 to 1,000 cPs. The apparent viscosity (Brookfield viscosity) of the olefin polymer composition (AM) at 150°C is a value measured by the method described in JIS K7117-1. The apparent viscosity of component (B) at 150°C is preferably 1 to 1,000 cPs, more preferably 5 to 800 cPs, and particularly preferably 5 to 50 cPs. When the apparent viscosity is within the above range, an excellent balance between low volatility, handleability, and dispersibility in water is achieved.

[0109] (AM3) The weight average molecular weight is 1,000 to 50,000. The weight average molecular weight (Mw) of the olefin polymer composition (AM) is a value obtained by measuring by gel permeation chromatography (GPC) according to the method described below and converting it into a standard polystyrene equivalent. The weight average molecular weight (Mw) of the olefin polymer composition (AM) is preferably 1,000 to 50,000, more preferably 1,000 to 30,000, further preferably 1,500 to 30,000, and particularly preferably 2,000 to 3,000. If the Mw is excessively below the above range, the composition may be easily flammable due to a large amount of easily volatile components, resulting in poor storage stability, or the evaporation loss in the aqueous dispersion may increase. If the Mw is excessively above the above range, the viscosity of the copolymer may increase, making it difficult to disperse uniformly in water.

[0110] (AM4) Molecular weight distribution is 2.5 or less. The molecular weight distribution of the olefin polymer composition (AM) is measured by gel permeation chromatography (GPC) according to the method described below, and is calculated as the ratio (Mw / Mn) of the weight average molecular weight (Mw) obtained by standard polystyrene conversion to the number average molecular weight (Mn). The Mw / Mn of the olefin polymer composition (AM) is preferably 2.5 or less, more preferably 2.3 or less, and even more preferably 2.0 or less. When the molecular weight distribution excessively exceeds the above range, it means that the polymer contains a large amount of low molecular weight components and high molecular weight components. When the polymer contains a large amount of low molecular weight components, it is likely to be flammable due to the large amount of easily volatile components, which may deteriorate the storage stability or increase the evaporation loss in the aqueous dispersion. When the polymer contains a large amount of high molecular weight components, the viscosity of the polymer increases, which may make it difficult to disperse uniformly in water. The weight average molecular weight and molecular weight distribution can be determined by gel permeation chromatography (GPC) under the conditions described in the Examples.

[0111] (AM5) No melting point is observed. The olefin polymer composition (AM) preferably has no observed melting point in differential scanning calorimetry (DSC). Here, "no observed melting point (Tm)" means that the heat of fusion (ΔH) (unit: J / g) measured by differential scanning calorimetry (DSC) is not substantially measured. "No substantially measured heat of fusion (ΔH)" means that no peak is observed in differential scanning calorimetry (DSC) or the observed heat of fusion is 1 J / g or less.

[0112] The melting point (Tm) and heat of fusion (ΔH) of the olefin polymer composition (AM) are determined by performing differential scanning calorimetry (DSC) and analyzing the DSC curve with reference to JIS K7121 when the composition is cooled to -100°C and then heated to 150°C at a heating rate of 10°C / min. If no melting point is observed, this means that the olefin polymer composition (AM) has low crystallinity, does not increase in viscosity, does not become solid, and has excellent dispersibility in water.

[0113] <Preparation of Water Dispersion Composition> The olefin polymer composition (AM) can be used to prepare an aqueous dispersion composition. In other words, the aqueous dispersion composition is a composition in which the olefin polymer composition (AM) is mixed with water and the olefin polymer composition (AM) is dispersed in water. If necessary, a known polymer such as the olefin polymer (A) may be used in combination. The amount of the polymer to be combined is preferably less than that of the olefin polymer composition (AM), specifically, 50% by mass or less of the olefin polymer composition (AM).

[0114] The aqueous dispersion composition preferably contains 0.01 to 50% by mass of the olefin polymer composition (AM), more preferably 0.05 to 30% by mass, and even more preferably 0.1 to 20% by mass. When the other polymer is used in combination, the total content of the other polymer and the olefin polymer composition (AM) is preferably within the above range.

[0115] The water content of the aqueous dispersion composition is preferably from 50 to 99.99% by mass, more preferably from 70 to 99.95% by mass, and further preferably from 80 to 99.9% by mass.

[0116] The method for producing the water dispersion composition may, for example, be a method in which water and the olefin polymer composition (AM) are emulsified by a conventional method using an emulsifier such as a homomixer, a colloid mill, a line mixer, a homogenizer, etc. The water temperature during emulsification is preferably 40 to 99°C, more preferably 50 to 95°C.

[0117] When morpholine is used in preparing an aqueous dispersion of the olefin polymer composition (AM), the morpholine reacts with the polar group of the olefin polymer composition (AM) to stabilize the aqueous dispersion. Morpholine may be added when preparing the aqueous dispersion, or may be mixed in advance with the olefin polymer composition (AM) and reacted. Morpholine is preferably added in an amount of 1 to 50 parts by mass, more preferably 1 to 30 parts by mass, and particularly preferably 2 to 20 parts by mass, per 100 parts by mass of the olefin polymer composition (AM).

[0118] The aqueous dispersion composition of the present invention may contain surfactants, corrosion inhibitors, antioxidants, animal and vegetable oils or their fatty acid esters, synthetic lubricating oils, waxes, inorganic powders, and various other components (including components generally referred to as additives). The above components may be used alone or in combination of two or more.

[0119] As the surfactant, various surfactants such as anionic, cationic, and nonionic surfactants can be used. For example, alkylene oxide adducts of nonylphenol, alkylene oxide adducts of linear higher alcohols having 12 to 18 carbon atoms, alkylene oxide adducts of higher amines, polyoxyethylene adducts of fatty acids such as castor oil, alkylene oxide adducts of fatty acid amides, alkyl sulfates, tamol type, tetraalkylammonium salts, and alkyl betaines can be exemplified. When a surfactant is used, the amount of the surfactant used is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, in the aqueous dispersion composition.

[0120] Examples of the corrosion inhibitor include sodium nitrite, sodium benzoate, triethanolamine salts, etc. When a corrosion inhibitor is used, the amount of the corrosion inhibitor added is preferably 0.01 to 10% by mass, and more preferably 0.1 to 5% by mass in the aqueous dispersion composition.

[0121] The antioxidant may be a phenolic compound such as 2,6-di-t-butyl-4-methylphenol or an amine compound. The amount of the antioxidant added is preferably 0 to 3% by mass in the aqueous dispersion composition.

[0122] Examples of the animal and vegetable oils include mineral oil, rapeseed oil, soybean oil, coconut oil, palm oil, beef tallow, lard, etc. Examples of the synthetic lubricating oils include polyalphaolefin, polybutadiene, polyisobutylene, various ester oils, etc.

[0123] Examples of waxes that can be used include synthetic waxes such as polyethylene wax and polypropylene wax, oxides and acid-modified products of these synthetic waxes, and natural waxes such as carnauba, montan, and beeswax, provided that the dispersibility in water and adhesion to the mold are not adversely affected.

[0124] Examples of inorganic powders include talc, mica, clay, organic clay, boronite, mortar, sericite, calcium carbonate, borate, alumina, titanium oxide, sodium bicarbonate, zirconium oxide, graphite, carbon black, and diamond powder.

[0125] Other components that may be used in combination include silicone compounds such as silicone, dimethyl silicone, alkyl-modified silicone, and alkylaralkyl-modified silicone; zinc dialkyldithiophosphate (ZnDTP), molybdenum dialkyldithiophosphate (MoDTP), zinc dithiocarbamate (ZnDTC), molybdenum dithiocarbamate (MoDTC), phosphorus-based and sulfur-based extreme pressure agents, antifoaming agents, and preservatives to reduce friction.

[0126] <Application> The aqueous dispersion composition can be used for printing inks, printing pastes, lacquers, coating agents for food packaging materials, coating agents for flooring materials, coating agents for shoes, coating agents for automobiles, finishing agents for papermaking, spinning, and textiles, cutting oils, release agents for die casting, etc. The aqueous dispersion composition has a molecular weight sufficient to ensure adhesion to a die when used as a release agent for die casting, a composition that does not easily cause accumulation of oxidized deterioration products, and contains a copolymer with excellent dispersibility in water, and therefore can be particularly suitably used as a release agent for die casting. EXAMPLES

[0127] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. [Measurement method] In the following examples and comparative examples, physical properties were measured by the following methods.

[0128] <Content of ethylene-derived structural units (mol%)> Using a JASCO Fourier transform infrared spectrophotometer FT / IR-610 or FT / IR-6100, the 721 cm -1 Absorption near 1155 cm due to propylene skeletal vibration -1 Absorbance ratio with absorption near 155cm -1 / D721cm -1 ) was calculated, and the content (mass%) of ethylene-derived structural units (hereinafter also referred to as ethylene units) was calculated from a calibration curve (prepared using a standard sample according to ASTM D3900) prepared in advance. Next, the content (mol%) of ethylene units was calculated using the obtained content (mass%) of ethylene units according to the following formula.

[0129]

number

[0130] <Viscosity characteristics> The kinematic viscosity at 100 °C was measured and calculated by the method described in JIS K2283. The apparent viscosity (Brookfield viscosity) at 150 °C was measured and calculated by the method described in JIS K7117-1.

[0131] <Molecular weight and molecular weight distribution> The molecular weight and molecular weight distribution were measured as follows using Tosoh Corporation's HLC-8320GPC. As separation columns, four TSKgel SuperMultipore HZ-M columns were used, the column temperature was set at 40 °C, tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the mobile phase, the elution rate was 0.35 ml / min, the sample concentration was 5.5 g / L, the sample injection volume was 20 microliters, and a differential refractometer was used as the detector. As the standard polystyrene, PStQuick MP-M manufactured by Tosoh Corporation was used. According to the procedure of universal calibration, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) were calculated in terms of polystyrene molecular weight, and the molecular weight distribution (Mw / Mn) was calculated from these values.

[0132] Using o-dichlorobenzene / benzene-d6 (4 / 1 [vol / vol%]) as the measurement solvent, under the measurement conditions of a measurement temperature of 120 °C, a spectral width of 250 ppm, a pulse repetition time of 5.5 seconds, a pulse width of 4.7 μsec (45° pulse), and an integration number of 500 or more (100 MHz, JEOL ECX400P), or under the measurement conditions of a measurement temperature of 120 °C, a spectral width of 250 ppm, a pulse repetition time of 5.5 seconds, a pulse width of 5.0 μsec (45° pulse), and an integration number of 10,000 or more (125 MHz, Bruker BioSpin AVANCEIII cryo-500) 13 the 13C-NMR spectrum was measured, and the B value was calculated based on the following formula (5). The peak assignment was performed with reference to the aforementioned known literature. B = P O1-O2 / (2 × P O1 × P O2 ) (5)

[0133] In the above formula (5), P O1represents the molar fraction of the structural unit derived from the first olefin, and P O2 represents the molar fraction of the structural unit derived from the second olefin, and P O1-O2 is the entire dyad chain The mole fraction of "first olefin-second olefin" sequence is shown.

[0134] <Unsaturated bond amount> 1H-NMR spectrum (400MHz, JEOL ECX400P) was measured using o-dichlorobenzene-d4 as the measurement solvent, with a measurement temperature of 120°C, a spectrum width of 20ppm, a pulse repetition time of 7.0 seconds, and a pulse width of 6.15μsec (45° pulse). The solvent peak (ortho-dichlorobenzene 7.1ppm) was used as the chemical shift standard, and the amount of unsaturated bonds per 1000 carbon atoms (units / 1000C) was calculated from the ratio of the integral value of the main peak observed at 0-3ppm to the peak derived from unsaturated bonds observed at 4-6ppm.

[0135] <Melting point> Using Seiko Instruments X-DSC-7000, about 8 mg of copolymer sample was placed in a simple sealed aluminum sample pan and placed in a DSC cell. The DSC cell was heated from room temperature to 150°C at 10°C / min under a nitrogen atmosphere, then held at 150°C for 5 minutes, then cooled at 10°C / min, and the DSC cell was cooled to -100°C (cooling down process). Next, after holding at -100°C for 5 minutes, the temperature was raised at 10°C / min, and the temperature at which the enthalpy curve obtained during the heating process showed a maximum value was taken as the melting point (Tm), and the sum of the endothermic heats associated with melting was taken as the heat of fusion (ΔH). If no peak was observed or the value of the heat of fusion (ΔH) was 1 J / g or less, the melting point (Tm) was considered not to be observed. The melting point (Tm) and heat of fusion (ΔH) were determined based on JIS K7121.

[0136] <Chlorine content> Using Thermo Fisher Scientific ICS-1600, the copolymer sample was placed in a sample boat and decomposed by combustion in an Ar / O2 gas stream at a furnace temperature of 900°C. The generated gas was absorbed in an absorbing liquid, and the amount of chlorine contained was quantified by ion chromatography.

[0137] How to determine (M) The content of maleic anhydride in the sample used to create the calibration curve was determined by elemental analysis (using a vario EL type device manufactured by Elementor Co., Ltd.) using the KBr thin film method and IR measurement using an FT-IR 4100 type infrared spectroscopy measuring device manufactured by JASCO Corp.

[0138] How to determine (MD) The weight fraction of the unreacted olefin polymer was measured using an HPLC apparatus (Alliance e2695 Separations Module / 2414 RI Detector) manufactured by Waters Corporation as follows. Mobile phase: Hexane Flow rate: 1ml / min Sample concentration: 1w / v% Sample injection volume: 20 μL Column: Normal phase column manufactured by Agilent Technologies, Inc. Column size: inner diameter 4.6 mm, length 250 mm Column packing material: Silica particles (particle size 5 μm) Detector; Differential refractometer The raw olefin polymer used in the examples of the present invention was used as a standard. The peak area (S0) (appearing in the region of 2 to 3.5 minutes) when the standard was measured under the above conditions was compared with the peak area (S MD ) is determined by the following formula: MD=100 × S MD / S0

[0139] <Acid value> A precisely weighed copolymer sample was dissolved in a mixed solvent of mixed xylene:n-butanol = 1:1 by mass ratio to obtain a sample solution. Next, this sample solution was titrated with a previously standardized N / 10 potassium hydroxide alcohol solution (7g of special grade potassium hydroxide was added with 5g of ion-exchanged water, and the volume was adjusted to 1L (liter) with primary ethyl alcohol, and the titer was standardized to F with N / 10 hydrochloric acid and 1% phenolphthalein solution), and the oxidation was calculated from the neutralization amount according to the following formula. Acid value (mgKOH / g) = (N / 10 KOH titration volume (ml) x F x 5.61) / (sample (g) x 0.01) The olefin polymer (A), organic acid compound (B) and radical initiator (C) used in the examples are shown below.

[0140] The following olefin polymer (A-1) was obtained by a method according to the conditions of Polymerization Example 1 in JP-A-2016-102157, and the following olefin polymer (A-2) was obtained by a method according to the conditions of Polymerization Example 2 in JP-A-2016-102157. Olefin polymer (A) Olefin polymer (A-1): Ethylene-propylene copolymer Ethylene unit content: 48.5 mol%, propylene content: 51.5 mol% Weight average molecular weight (Mw): 5,170 Molecular weight distribution (Mw / Mn)1.7 Olefin polymer (A-2): Ethylene-propylene copolymer Ethylene unit content: 53.1 mol%, propylene content: 46.9 mol% Weight average molecular weight (Mw): 8,560 Molecular weight distribution (Mw / Mn): 1.8

[0141] Organic acid compound (B) Maleic anhydride: (Fujifilm Wako Pure Chemical Industries, Ltd.) Wako special grade Radical initiator (C) Di-t-butyl peroxide (Perbutyl D manufactured by NOF Corporation) 1.5 hour half-life temperature: 144.1℃, 10.5 hour half-life temperature: 123.7℃ The basic procedures for producing the olefin polymer compositions carried out in the examples are as follows.

[0142] <Basic operations for producing olefin polymer compositions> The olefin polymer (A-1) was charged at 95.5 parts by mass and the olefin polymer (A-2) was charged at 4.5 parts by mass in a reactor equipped with a nitrogen inlet tube, a water-cooled condenser, a thermometer, a maleic anhydride supply device and a radical generator supply device, and the temperature was raised. After purging the oxygen in the system by introducing nitrogen into the reactor at 120°C, the system was kept at 160°C. Then, maleic anhydride (about 70°C: liquid) and di-t-butyl peroxide were fed to the reactor for a predetermined time at a predetermined rate, and after the feeding was completed, the reactor was kept at 160°C for another hour and stirring was continued. The sum of the feeding time of each component and the subsequent holding time was defined as the reaction time.

[0143] Next, the temperature inside the reactor was further raised to 175°C, and the pressure inside the system was released, after which unnecessary components (unreacted maleic anhydride and decomposition products of di-t-butyl peroxide, etc.) were removed under reduced pressure and nitrogen flow conditions.

[0144] (Examples 1 to 5) According to the basic procedure for producing the olefin polymer composition described above, the olefin polymer compositions were produced under various production conditions shown in Table 1. The results are shown in Table 1.

[0145] [Table 1]

[0146] The manufacturing methods of Examples 1 to 5 all meet the parameters of the present invention. Examples 4 and 5 are larger in scale than Examples 1 to 3. As can be seen from the results in Table 1, by producing an olefin polymer composition using the parameters of the present invention, it is possible to produce an olefin polymer composition having a specific unreacted olefin polymer content (MD) at will, and by appropriately changing the parameters, it is possible to produce olefin polymer compositions having different unreacted olefin polymer contents (MD).

[0147] FIG. 1 shows the parameters (Aw (2 / 3) / (Bw × VA (1 / 4) 2 is a graph showing the relationship between the parameter (Aw (2 / 3) / (Cw × VA (1 / 4) )) and the unreacted olefin polymer content (MD).

[0148] As shown in Figures 1 and 2, the parameters of the present invention and the content of unreacted olefin polymer (MD) show a relatively good correlation regardless of the production scale. Therefore, the production method using the parameters of the present invention can easily set the production conditions for olefin polymer compositions having various different contents of unreacted olefin polymer. Such a method can easily set the production conditions at the stage of scaling up from laboratory scale conditions, and can be said to be useful for producing olefin polymer compositions at various scales.

Claims

1. A method for producing an olefin polymer composition (AM) containing a structural unit derived from an organic acid compound (B), comprising contacting an olefin polymer (A), an organic acid compound (B), and a radical initiator (C) in a reactor in a flowing state under conditions that satisfy the following requirements (X1) to (X3): (X1) The fluidized state satisfies the condition represented by the following formula (1). 0.01<(AA) (2 / 3) / (Tw×V｡ (1 / 4) ))<100 …(1) Here, Aw, Bw and VA are defined as follows: Aw: content per volume of the olefin polymer (A) in a fluid state (g / cm 3 )and, The product of the linear velocity (cm / hour) of the olefin polymer (A) in a fluidized state (g / cm 2 ·time) Bw: Supply rate per unit area of ​​organic acid compound (B) per hour (g / cm 2 ·time) VA: the volume (m ) of the liquid containing the olefin polymer (A) in a fluidized state present in the reactor 3 ) (X2) The temperature (T) (°C) when the olefin polymer (A), the organic acid compound (B), and the radical initiator (C) are contacted and the 1.5-hour half-life temperature (T1) (°C) of the radical initiator (C) satisfy the relationship represented by the following formula (2). T1<T<(T1+60)...(2) (X3) The time for which the olefin polymer (A), the organic acid compound (B) and the radical initiator (C) are contacted is within the range of 1 to 20 hours.

2. The process for producing an olefin polymer composition (AM) according to claim 1, wherein the olefin polymer (A) satisfies the following requirements (A1) and (A2): (A1) Contains structural units derived from ethylene and structural units derived from an α-olefin having 3 or more carbon atoms, and the content of the structural units derived from ethylene is 10 to 85 mol % (wherein the total of the structural units derived from ethylene and the structural units derived from the α-olefin is 100 mol %). (A2) The weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is 1,000 to 50,000, and the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn value) is 2.5 or less.

3. The method for producing the olefin polymer composition (AM) according to claim 1, which further satisfies the following requirement (X4): (X4) The fluidized state satisfies the condition represented by the following formula (3). 0.1<(AW) (2 / 3) / (Cw×VA (1 / 4) ))<1000 …(3) Cw: Supply rate per unit area of ​​the radical initiator (C) (g / cm 2 ·time)

4. The process for producing an olefin polymer composition (AM) according to claim 1, wherein the olefin polymer composition (AM) satisfies the following requirements (M1) and (M2). (M1) The mass content (M) of the structural unit derived from an organic acid compound in the olefin polymer composition (AM) is 0.2 to 22 mass% (wherein the olefin polymer composition (AM) is taken as 100 mass%). (M2) The content (MD) of the unreacted olefin polymer (AR) contained in the olefin polymer composition (AM) and the mass content (M) of the structural unit derived from the organic acid compound satisfy the relationship represented by the following formula (4). -4.0 x (M) + 90 ≧ (MD) ≧ -4.0 x (M) + 60 ... (4)

5. The process for producing an olefin polymer composition (AM) according to claim 1, wherein the organic acid compound (B) is a compound (B1) selected from unsaturated carboxylic acids or acid anhydrides thereof.

6. The process for producing an olefin polymer composition (AM) according to claim 1, wherein the organic acid compound (B) is maleic acid and / or maleic anhydride.

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