METHOD FOR PREPARING SUPPORTED METALLOCENE CATALYST AND METHOD FOR PREPARING POLYOLEFIN USING THE SAME

摘要

The present invention relates to a method for preparing a supported metallocene catalyst, and a method for preparing polyolefin using the same, in which the supported metallocene catalyst prepared from the simple process according to the method for preparing the supported metallocene catalyst of the present invention can apply to the polymerization of the polyolefin that is polymerized at low pressure or high pressure; the molecular weight distribution of polyolefin prepared can be easily controlled; and there are effects such that its catalyst activity is significantly higher than that of the existed supported metallocene catalyst, and the molecular weight distribution can be easily controlled.

主权项

1. A method for preparing a supported metallocene catalyst, comprising:
i) preparing the support supported with co-catalyst by reacting the support with co-catalyst 1; ii) preparing a catalyst precursor that is gradually supported with the co-catalyst and the metallocene compound in the support by reacting the metallocene copound and the support supported with the co-catalyst; and iii) preparing the metallocene catalyst by reacting the catalyst precursor and co-catalyst 2; in which the metallocene compound is one or more selected from the group consisting of the compounds represented by the following Chemistry Figure 1 to Chemistry Figure 3: [In the above Chemistry Figure 1, 2 or 3, Cp and Cp′ are the same or different one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluororenyl radical to each other; Rm and Rn are the same or different hydrogen radical, alkyl radical of carbon number 1˜20, cycloalkyl radical of carbon number 3˜23, aryl radical of carbon number 6˜26, alkenyl radical of carbon number 2˜22, alkylaryl radical of carbon number 7˜27, arylalkyl radical of carbon number 7˜27, arylalkenyl radical of carbon number 8˜28 or alkylsilyl radical of carbon number 1˜20; R1 and R2 are the same or different hydrogen radical or hydrocarbyl radical of carbon number 1˜6; a, a′, b or b′ are an integer of 1˜4, respectively; M is a transition metal in group 4B, group 5B or group 6B of the periodic table; Q is a halogen radical, or alkyl radical of carbon number 1˜20, alkenyl radical of carbon number 2˜22, aryl radical of carbon number 6˜26, alkylaryl radical of carbon number 7˜27, arylalkyl radical of carbon number 7˜27; or alkylidene radical of carbon number 1˜20, k is 2 or 3, z is 0 or 1, and when k is 3, z is 0; B is one selected from the group consisting of alkyl radical of carbon number 1˜4, or hydrocarbyl radical including silicon, germanium, phosphorus, nitrogen, boron or aluminum; In the Chemistry Figure 3, J is one selected from the group consisting of NRs, O, PRs and S, the Rs is alkyl radical of carbon number 1˜20 or substituted alkyl radical; Any one of hydrogen radical located at the Rm, Rn, B or Rs is the compound represented by Chemistry Figure 4, 5 or 6] [In the above Chemistry Figure 4, Z is oxygen atom or sulfur atom, and preferably oxygen atom; R and R′ are the same or different hydrogen radical; alkyl radical of carbon number 1˜20, cycloalkyl radical of carbon number 3˜23, aryl radical of carbon number 6˜26, alkenyl radical of carbon number 2˜22, alkylaryl radical of carbon number 7˜27, arylalkyl radical of carbon number 7˜27, arylalkenyl radical of carbon number 8˜28, or preferably the same or different alkyl radical of carbon number 1˜20; two of R′ may be connected to each other to form a ring; G is alkoxy radical of carbon number 1˜20, aryloxy of carbon number 6˜26, alkylthio of carbon number 1˜20, arylthio of carbon number 6˜26, phenyl or substituted phenyl of carbon number 1˜20, or preferably alkoxyl of carbon number 1˜20, and may be connected to R′ to form a ring; When Z is sulfur atom, G should be alkoxy or aryloxy; When G is alkylthio, arylthio, phenyl or substituted phenyl, Z should be oxygen atom] [In the above Chemistry Figure 5, Z′ is oxygen atom or sulfur atom, or preferably oxygen atom, at least one of two Z′ is oxygen atom; R and R″ are the same or different alkyl radical of carbon number 1˜20, cycloalkyl radical of carbon number 3˜23, aryl radical of carbon number 6˜26, alkenyl radical of carbon number 2˜22, alkylaryl radical of carbon number 7˜27, arylalkyl radical of carbon number 7˜27, arylalkenyl radical of carbon number 8˜28, or preferably the same or different alkyl radical of carbon number 1˜20; two of R′ may be connected to each other to form a ring; R and R″, or two R″s may be connected to each other to form a ring] [In the above Chemistry Figure 6, Z″ is oxygen, sulfur, nitrogen, phosphorus or arsenic atom, or preferably oxygen atom; R″′ is the same or different hydrogen radical, alkyl radical of carbon number 1˜40, cycloalkyl radical of carbon number 3˜43, aryl radical of carbon number 6˜46, alkenyl radical of carbon number 2˜42, alkylaryl radical of carbon number 7˜47, arylalkyl radical of carbon number 7˜47 or arylalkenyl radical of carbon number 8˜48 to each other, preferably the same or different alkyl radical of carbon number 1˜40 to each other; R″′ is hydrogen radical, alkyl radical of carbon number 1˜40, aryl radical of carbon number 6˜46, alkenyl radical of carbon number 2˜42, alkyaryl radical of carbon number 7˜47, alkylsilyl radical of carbon number 1˜40, arylsilyl radical of carbon number 6˜46, phenyl or substituted phenyl of carbon number 6˜46 to each other, preferably alkyl radical of carbon number 1˜40; n is 1 or 2, or preferably 1, when Z″ is oxygen or sulfur, n is 1; when Z″ is nitrogen, phosphorus or arsenic, n is 2]