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    • 专利摘要:
    PURPOSE: An olefin copolymer with a high content of a polar monomer, its preparation method, an olefin copolymer ionomer containing a metal salt and its preparation method are provided, to improve the polymerization velocity and the activity and to increase the content of carboxylic acid inside the polar copolymer. CONSTITUTION: The olefin copolymer is prepared by copolymerizing the α-olefin monomer represented by CH2=CH-R (wherein R is H or a linear, branched or cyclic alkyl group of C1-C10), the unsaturated carboxylic acid polar monomer represented by CH2=CH(CH2)nCOOH (wherein n is an integer of 3-17) and the α-olefin monomer represented by CH2=CH=R (wherein R is H or a linear, branched or cyclic alkyl group of C1-C12), in the presence of a Ziegler-Natta catalyst and an organic aluminium compound. The olefin copolymer ionomer is prepared by crosslinking the olefin copolymer with a metal salt.
    公开号:KR20030041222A
    申请号:KR1020010071862
    申请日:2001-11-19
    公开日:2003-05-27
    发明作者:강갑구；정영태；이동호
    申请人:대한유화공업 주식회사；
    IPC主号:
    专利说明:

    Olefin Copolymer Containing High Polar Group, the Process for the Preparation Thereof and Olefin Copolymer Ionomer with Metal Salt}
    [5] The present invention relates to an olefin copolymer having a high content of a polar monomer, a method for preparing the same, and an olefin copolymer ionomer containing a metal salt. More specifically, a third monomer is prepared by polymerizing an α-olefin monomer and a polar monomer. The present invention relates to an olefin copolymer having a high content of polar monomer, a method for preparing the same, and an olefin ionomer in which the polymer chain of the olefin copolymer is crosslinked with a metal salt.
    [6] In general, polyolefins such as polyethylene and polypropylene are lighter than other known synthetic resins and are widely used as materials for manufacturing various molded articles from fibers and films because of their excellent mechanical strength and elasticity. However, as expected from the chemical structure of polyolefin, it is chemically inert because it does not have a polar atom group, which is why dyeing, printability, adhesiveness, etc. have little property, and the bloom phenomenon such as additives is a defect. There is this.
    [7] In order to solve this problem, there is a method of chromic acid solution treatment, ozonation, corona discharge treatment, or grafting monomers containing polar groups to activate the resin surface, but it is not sufficient.
    [8] Referring to US Patent No. 3,264,272 as a specific example of a conventional method for preparing an ionomer resin, a liquid base metal compound such as caustic soda is incorporated into an ethylene-methacrylic acid copolymer produced by radical copolymerization of ethylene and methacrylic acid. It is manufactured using a roll mill. In addition, US Patent No. 3,437,718 adopts a method of obtaining an ionomer through a roll mill operation at high temperature using methyl sodium, zinc acetate, etc. as a metal neutralizing agent in the ethylene-methacrylic acid copolymer.
    [9] However, the production of ionomers by the above-described method is not only difficult to handle raw materials, but also difficult to obtain a product having uniform physical properties.
    [10] In addition, US Patent No. 3,404,134 discloses a slurry obtained by melting an ethylene-methacrylic acid copolymer made by radical copolymerization of ethylene and methacrylic acid with molten hexamethylenediamine, and then washing the precipitate formed by adding a non-solvent such as methanol. Although attempting a manufacturing method, there is a disadvantage in that a device for separating the ionomer generated by precipitation with the solvent as well as a risk to the safety of the operator due to the toxicity of the solvent has a disadvantage.
    [11] In order to solve the above problems, US Pat. No. 3,969,434 proposes a method for producing an ionomer by causing a neutralization reaction in a conventional extruder using zinc formic acid, which is a highly reactive metal ion crosslinking agent.
    [12] In Korean Patent No. 93-6911, an ethylene-methacrylic acid copolymer is applied to polyethylene melt-kneaded with a metal salt in order to prevent the remaining amount of the unreacted metal compound due to the local oversupply of the active agent without disturbing the electrostatic bonding. The method of producing an ionomer using water or acetic acid as a reaction activator while melt-kneading at high temperature is shown.
    [13] On the other hand, Korean Patent No. 99-25669 discloses glycidyl methacrylate (Glycidyl methacrylate) in order to increase the compatibility of the polypropylene resin and the ionomer as a main component of the ionomer, an acrylic acid-ethylene copolymer neutralized with polypropylene and metal ions. A method for preparing a resin having excellent scratch resistance, impact strength and gloss by combining a polypropylene resin grafted with a polypropylene resin or a maleic anhydride (maleicanhydride) is grafted.
    [14] In addition, Korean Patent No. 10-197478 proposes a method for preparing ionomers of low molecular weight copolymer amides by reacting a copolymeric acid of alpha olefin and unsaturated carboxylic acid with at least one amino acid compound.
    [15] However, the above grafting methods do not yield satisfactory results for activating the resin surface. A fundamental solution is to prepare a polar polymer by copolymerizing an alkene compound containing a polar group and an olefin. However, in general, Ziegler-Natta catalysts are copolymerized because the activity of the catalyst is reduced by the polar group-containing compound. There is a need for a method of keeping the catalytic activity high enough during the reaction. As an example, U.S. Patent No. 3,492,277 selected undecylene polar derivatives in which olefinic double bonds are isolated away from the polar group in order to increase the polymerization reactivity between the Ziegler-Natta catalyst and the polar monomer. The acid, amide, and polar groups were first blocked with alkyl aluminum, and then copolymerized with olefin and a catalyst to synthesize a polar group-containing copolymer.
    [16] U.S. Patent No. 3,761,458 discloses a catalyst and excess by using derivatives such as N, N-dinormbutyl-10-undecenamine substituted with alkyl having high steric hindrance to the polar group of the polar monomer for polymerization of the polar monomer and the olefin monomer. In the presence of an alkyl aluminum cocatalyst of, random and block copolymerization with an olefin is carried out to prepare a polar copolymer.
    [17] The present invention copolymerizes the unsaturated carboxylic acid polar monomer of the following general formula (2) as the second monomer and the α-olefin monomer of the following general formula (1) as the first monomer to produce the copolymer. It is an object of the present invention to provide a copolymerized olefin copolymer having a content of an unsaturated carboxylic acid polar monomer by addition of an α-olefin monomer of a) and a method for producing the same.
    [18] It is another object of the present invention to provide an olefin ionomer containing a metal salt by crosslinking with an olefin copolymer having a high content of a polar monomer with a metal salt.
    [19] CH 2 = CH-R ...... (1)
    [20] CH 2 = CH (CH 2 ) n CO 2 H ... (2)
    [21] CH 2 = CH-R ...... (3)
    [22] In General Formula (1), R is one selected from hydrogen and a linear, cyclic, or branched linear alkyl group having 1 to 10 carbon atoms.
    [23] In General Formula (2), n is an integer of 3 ≦ n ≦ 17.
    [24] In General Formula (3), R is one selected from hydrogen and a linear, cyclic, or branched linear alkyl group having 1 to 12 carbon atoms.
    [1] 1 (a) is an infrared spectrum result of propylene / hexene copolymer,
    [2] (b) is an infrared spectrum result of the propylene / hexene / undecenoic acid polar copolymer,
    [3] (c) is an infrared spectrum result of the zinc salt ionomer of the propylene / hexene / undecenoic acid polar copolymer.
    [4] 2 is a graph showing the results of nuclear magnetic resonance (NMR) of the propylene / hexene / undecenoic acid polar copolymer.
    [25] The olefin copolymer having a high content of the polar monomer of the present invention is an α-olefin monomer of the following general formula (1) as the first monomer, an unsaturated carboxylic acid polar monomer of the following general formula (2) and the third monomer as the second monomer. The α-olefin monomer of the general formula (3) is a copolymer copolymerized.
    [26] CH 2 = CH-R ...... (1)
    [27] CH 2 = CH (CH 2 ) n CO 2 H ... (2)
    [28] CH 2 = CH-R ...... (3)
    [29] In General Formula (1), R is one selected from hydrogen and a linear, cyclic, or branched linear alkyl group having 1 to 10 carbon atoms.
    [30] In General Formula (2), n is an integer of 3 ≦ n ≦ 17.
    [31] In General Formula (3), R is one selected from hydrogen and a linear, cyclic, or branched linear alkyl group having 1 to 12 carbon atoms.
    [32] The method for producing an olefin copolymer having a high content of a polar monomer according to the present invention is the α-olefin monomer of Formula (1) as the first monomer and the second monomer as the first monomer in the presence of a Ziegler-Natta catalyst and an organoaluminum compound. In the polymerization of the unsaturated carboxylic acid polar monomer of (2) as the third monomer, the addition of the α-olefin monomer of the general formula (3) may increase the polymerization rate and activity in the copolymerization method for preparing a conventional polar copolymer.
    [33] On the other hand, the present invention is characterized in that the unsaturated carboxylic acid polar monomer and the organoaluminum compound are first reacted to increase the polymerization reactivity of the unsaturated double bond portion of the unsaturated carboxylic acid polar monomer of the general formula (2).
    [34] When the unsaturated carboxylic acid polar monomer, which is the second monomer represented by the above-mentioned general formula (2), is directly introduced into the polymerization reactor like the general monomer, the polymerization reaction with the double bond, which is the unsaturated catalyst of the titanium catalyst and unsaturated carboxylic acid, which causes polymerization, is a main catalyst. Rather, it reacts with the hydroxyl group (-OH) of the carboxylic acid to form a titanium complex, and titanium completely loses its activity as a polymerization catalyst.
    [35] To solve this problem, by converting the hydroxyl group having strong electron donor property of unsaturated carboxylic acid into oxygen-aluminum (O-Al) bond, not only disperses electron donor property of hydroxyl group in Al but also has steric hindrance effect, thus forming titanium complex of carboxylic acid. The process is suppressed and the reactivity of the unsaturated double bonds becomes relatively high, allowing titanium to remain active as a polymerization catalyst. An organoaluminum compound is used in the present invention for forming O-Al bonds, and the reaction scheme is as follows.
    [36] That is, in the present invention, the method for preparing an olefin copolymer is characterized in that polymerization is performed after blocking an unsaturated carboxylic acid, which is a second monomer, with an organoaluminum compound in the presence of a catalyst.
    [37] CH 2 = CH (CH 2 ) n CO 2 H + (C 2 H 5 ) 2 AlCl → CH 2 = CH (CH 2 ) n COOAl (C 2 H 5 ) Cl + C 2 H 6
    [38] Examples of the first monomer and the third monomer used in the polymerization of the present invention are ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, vinylcyclohexane, and 2-ethylhexene. , 1-octene, and the like, and examples of the second monomer which is an unsaturated carboxylic acid may include hexenoic acid, octenoic acid, decenoic acid, and undecenoic acid.
    [39] Examples of cocatalysts include diethylaluminum chloride, ethylaluminum dichloride, dinormalylaluminum chloride, diisobutylaluminum chloride, triethylaluminum, triisobutylaluminum, trinormal hexyl aluminum, trinormal maltyl aluminum, and trinormalmal decyl aluminum. It can select from organoaluminum compounds and can use.
    [40] Meanwhile, the catalyst used in the present invention may be selected from titanium trichloride catalyst, solbay type titanium trichloride catalyst, titanium tetrachloride catalyst, silica-supported titanium catalyst or magnesium-supported titanium catalyst.
    [41] In preparing an olefin copolymer comprising a polar monomer of the present invention, an organoaluminum compound, a polar monomer in which an unsaturated carboxylic acid and an organoaluminum compound are bonded, an α-olefin tertiary monomer of the general formula (3), and the general formula (1) The copolymerization of the α-olefin first monomer in the catalyst is carried out by the general polymerization method of α-olefin, and the temperature and pressure are not particularly limited, but the polymerization temperature is 30 to 150 ° C. and the pressure is 0.1 to 30 kg / cm. The range of 2 is suitable for copolymer production.
    [42] In addition, the present invention can be obtained by reacting the olefin copolymer prepared above with the metal salt solution at 50 to 70 ℃ for 20 to 40 hours, filtered and dried to obtain a metal salt ionomer containing the olefin copolymer.
    [43] In the metal salt solution used in the crosslinking, the metal of the metal salt may be a metal of Group IA, Group IIA or Group IIIA and Group IB to Group B of the chemical periodic table. Examples of such metals include metals of Groups IA, IIA, or IIIA, which are transition metals of sodium (Na), potassium (K), magnesium (Mg), calcium (Ca), gallium (Ga), and Groups IB to VB. As the copper, copper (Cu), silver (Ag), zinc (Zn), cadmium (Cd) or the like can be used.
    [44] Hereinafter, the present invention will be described in more detail with reference to the following examples and comparative examples. The following examples and comparative examples are only intended to illustrate the invention and do not limit the scope of the invention.
    [45] Example 1 Aluminum Blocking of Unsaturated Carboxylic Acids
    [46] A 1 L four-necked round bottom flask equipped with a magnetic stirrer, condenser and temperature sensor was placed in an ice bath and stirred with 523 ml (0.45 mol) of 15 wt% diethylaluminum chloride dissolved in hexane under a stream of nitrogen. 77.4 g (0.42 mol) of 10-undecenoic acid dissolved in 100 mL of hexane was added slowly through the dropping funnel.
    [47] After the step, the reaction mixture was heated at 55 ° C. for 1 hour to obtain ethylchloroaluminum-10-undecenoate (Ethylchloroaluminum-10-undecenoate, ECAU), which is a carboxylic acid complex substituted with dark orange aluminum.
    [48] Example 2 Polypropylene Copolymerization
    [49] After fully replacing the 1.6 L stainless steel autoclave with nitrogen, adding 500 ml of normal hexane and stirring 1.4 g of diethylaluminum chloride under a nitrogen stream, and stirring 14 g of the polar monomer ECAU prepared in Example 1, the third monomer 10 ml of 1-hexene are added sequentially.
    [50] Then, after nitrogen was removed using a vacuum pump, the temperature was raised to 50 ° C., and propylene, a first monomer, was added to a solvent of normal hexane until the propylene was completely saturated using a mass flow controller. 0.4 g of a Solvay titanium trichloride catalyst was added to carry out polymerization. At this time, propylene was continuously supplied for 2 hours while maintaining the polymerization temperature at 50 ° C. and the pressure at 0.3 kg / cm 2.
    [51] After the completion of the polymerization, the unreacted gas was slowly discharged, the reactor was opened, the slurry was poured into water containing 0.5 wt% hydrochloric acid, stirred at 40 ° C. for at least 1 hour, and the obtained polymer was filtered and washed with water and ethanol. Then dried at 40 ° C. in vacuo for 24 h.
    [52] The activity of the polar polypropylene polymer obtained by drying was 46.8 g-polymer / g-catalyst, the content of the polar group carboxylic acid was 3.3% by weight, the melting point temperature (Tm) and the crystallization temperature (Tc) of 150/104 ° C, respectively.
    [53] After pressing the obtained copolymer by pressing to make a film, the infrared spectrum (IR) was measured. In addition to the absorption peaks of polypropylene and hexene (see FIG. 1 (a)), a carboxylic acid peak was observed around 1750 cm −1 , and thus a polar copolymer was obtained. Was confirmed (see FIG. 1 (b)).
    [54] In addition, the results of nuclear magnetic resonance (NMR) measurements, in addition to the main peaks of polypropylene (21.8 ppm, 28.9 ppm, 46.5 ppm), 14.1 ppm, 23.4 ppm peak corresponding to hexene and 25.3 ppm, 34.5 ppm peak corresponding to undecenoic carboxylic acid. Was confirmed (see FIG. 2).
    [55] The measurement results for the polypropylene copolymer are summarized in Table 1 below.
    [56] <Examples 3 to 8>
    [57] A polypropylene copolymer was prepared under the same conditions as in Example 2 except that the amount of the polar monomer ECAU, 1-hexene, which is a third monomer, was used according to the Examples of Table 1 below. The results are summarized in Table 1 below.
    [58] Comparative Example 1
    [59] A polypropylene copolymer was prepared under the same conditions as in Example 2, except that the third monomer 1-hexene was used, and the amount of the polar monomer ECAU was used according to Table 1 below. The results are summarized in Table 1 below.
    [60] Comparative Example 2
    [61] A polypropylene copolymer was prepared under the same conditions as in Example 2 except that the polar monomer ECAB (Ethylchloroaluminum-3-butenoate), the third monomer, 1-hexene was used according to Table 1 below. The measurement results for are summarized in Table 1 below.
    [62] <Table 1> Measurement result (1) according to polymer polymerization of Example 2 to Comparative Example 2
    [63] ItemEUCA * (g)1-hexene (ml)activation**Carboxylic Acid Content in Polymers (wt%)Tm / Tc (℃) Example 2141046.83.3150/104 Example 3141855.55.4149/98 Example 4142262.06.5151/99 Example 5143555.47.2148/92 Example 6145054.811.1150/97 Example 772566.75.1150/98 Example 8282559.19.4150/100 Comparative Example 114020.43.1161/117 Comparative Example 214 ***10-****--
    [64] * ECAU: Ethylchloroaluminum-10-undecenoate
    [65] ** Activity: g-polymer / g-catalyst
    [66] *** Ethylchloroaluminum-3-butenoate (ECAB) instead of ECAU as polar monomer
    [67] ****-: Not measurable
    [68] Example 9
    [69] 150 ml of a 15 wt% zinc dichloride (ZnCl 2 ) aqueous solution was first added to a 250 ml glass reactor, and then 5 g of the polar polypropylene copolymer obtained in Example 6 was added thereto, reacted at 55 ° C. for 24 hours, filtered and washed with water. Drying in vacuo for 24 hours to obtain a metal salt (ionomer).
    [70] Infrared spectrum (IR) measurement of the obtained polymer showed that the peak of the carboxylic acid near 1750 cm −1 mentioned in Example 2 disappeared and the carboxylic acid peak near 1600 cm −1 was observed (see FIG. 1 (c)). Was 98.2% and Tm / Tc was 156 ℃ / 104 ℃, up 6 ℃ and 7 ℃ respectively.
    [71] <Example 10>
    [72] The experiment was carried out in the same manner as in Example 9 except that the polar polypropylene copolymer of Example 8 was used. The conversion rate to metal salt was 98% and Tm / Tc was increased by 6 ℃ to 156 ℃ / 106 ℃, respectively.
    [73] The present invention is characterized in the addition of an α-olefin monomer as a third monomer in the preparation of a copolymer containing a polar monomer in the preparation of a copolymer containing a polar monomer. Therefore, the polymerization rate and activity as well as the content of carboxylic acid in the polar polymer are proportionally increased by the comonomer effect by the addition of the third monomer of the present invention than in the conventional copolymerization method for preparing the polar copolymer. .
    权利要求:
    Claims (7)
    [1" claim-type="Currently amended] In the presence of a Ziegler-Natta type catalyst and an organoaluminum compound, the -Olefin monomer of the following general formula (1) as the first monomer and the unsaturated carboxylic acid polar monomer of the following general formula (2) as the second monomer are used as the third monomer A method for producing an olefin copolymer having a high content of polar monomers, which is copolymerized by addition of the α-olefin monomer of (3).
    CH 2 = CH-R ...... (1)
    CH 2 = CH (CH 2 ) n CO 2 H ... (2)
    CH 2 = CH-R ...... (3)
    In General Formula (1), R is one selected from hydrogen and a linear, cyclic, or branched linear alkyl group having 1 to 10 carbon atoms.
    In General Formula (2), n is an integer of 3 ≦ n ≦ 17.
    In General Formula (3), R is one selected from hydrogen and a linear, cyclic, or branched linear alkyl group having 1 to 12 carbon atoms.
    [2" claim-type="Currently amended] The method for producing an olefin copolymer having a high content of polar monomers according to claim 1, wherein the unsaturated carboxylic acid monomers of the general formula (2) used for copolymerization are first reacted with an organoaluminum compound and then copolymerized.
    [3" claim-type="Currently amended] The organoaluminum compound according to claim 1 or 2, wherein the organoaluminum compound is diethylaluminum chloride, ethylaluminum dichloride, dinormalbutylaluminum chloride, diisobutylaluminum chloride, triethylaluminum, triisobutylaluminum, trinormalhexyl aluminum, Method for producing a copolymer, characterized in that any one selected from tri-normal octyl aluminum, tri-normal decyl aluminum
    [4" claim-type="Currently amended] The method according to claim 1, wherein the catalyst is a titanium trichloride catalyst, a solbay type titanium trichloride catalyst, a titanium tetrachloride catalyst, a silica-titanium catalyst, or a magnesium-supported titanium catalyst.
    [5" claim-type="Currently amended] The method for producing a copolymer according to claim 1, wherein the content of the carboxylic acid polar group in the polar polymer is increased by the addition of the third monomer of the general formula (3).
    [6" claim-type="Currently amended] Method for producing an olefin copolymer ionomer containing a metal salt obtained by crosslinking a copolymer prepared by the method of any one of claims 1 to 4.
    [7" claim-type="Currently amended] The metal salt-containing olefin air according to claim 6, wherein the metal of the metal salt used for crosslinking is any one selected from transition metals of Group IA, Group IIA, Group IIIA Metals, Groups IB to VIIIB of the Chemical Periodic Table. Method of Preparation of Copolymer Ionomer
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    同族专利:
    公开号 | 公开日
    KR100462840B1|2004-12-20|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2001-11-19|Application filed by 대한유화공업 주식회사
    2001-11-19|Priority to KR10-2001-0071862A
    2003-05-27|Publication of KR20030041222A
    2004-12-20|Application granted
    2004-12-20|Publication of KR100462840B1
    优先权:
    申请号 | 申请日 | 专利标题
    KR10-2001-0071862A|KR100462840B1|2001-11-19|2001-11-19|Olefin Copolymer Containing High Polar Group, the Process for the Preparation Thereof and Olefin Copolymer Ionomer with Metal Salt|
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