CN100338107C - Hydroxy terminated polypropylene and its preparing method - Google Patents
Hydroxy terminated polypropylene and its preparing method Download PDFInfo
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- CN100338107C CN100338107C CNB2004100099066A CN200410009906A CN100338107C CN 100338107 C CN100338107 C CN 100338107C CN B2004100099066 A CNB2004100099066 A CN B2004100099066A CN 200410009906 A CN200410009906 A CN 200410009906A CN 100338107 C CN100338107 C CN 100338107C
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- metallocene catalyst
- hydroxy group
- terminal hydroxy
- promotor
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Abstract
The present invention relates to hydroxy terminated polypropylene and a preparing method thereof. One end of a macromolecular chain is provided with polypropylene with a hydroxy base group; the structural general formula is disclosed in the specification, wherein n is any whole number within a range of 100 to 100000. a catalyst system which is composed of a metallocene catalyst and alkyl aluminoxane is used for catalyzing the polymerization of propylene; after the polyreaction is finished, dry air or oxygen is led in a reacting system; finally, water solutions of hydrogen peroxide and basic hydroxide are added for processing to obtain polypropylene having a macromolecular chain whose one end is provided with a hydroxy base group. The method has the characteristics of high functionality (which is larger than or equal to 0.8) of a medium-end hydroxy group of prepared polymers, high isotactic spatial configuration of polymers, larger adjustment range of molecular weight, narrow molecular weight distribution, simple preparation method, etc.
Description
Technical field
The present invention relates to a kind of terminal hydroxy group polypropylene and preparation method thereof.
Background technology
Polyolefine is to use general-purpose plastics kind very widely at present.But, cause its cementability, printing and dyeing property and very poor, thereby limited polyolefinic range of application with the consistency of other material owing to do not have any polar group on the polyolefine macromolecular chain.
The method of existing polyolefin functional modification comprises, free radical grafting (Tao Si equality, Chinese plastics .2002,16 (5): 1; Wan Weitao etc., 11), crosslinked (Shu Wenyi, plastics .1992,21 (5): 29 New Chemical Materials .2003,31 (8):; Shen Jingshu etc., polymer circular .1992,3:170), Cement Composite Treated by Plasma (Zhang Lihui etc., plastics industry .2003,31 (6): 17) etc., but these methods can not be controlled the structure of product accurately, but also have a lot of side reactions, cause polyolefin structure to change (as producing crosslinked or degraded), cause its mis-behave.
The synthetic polyolefinic method of end group functional mainly contains two kinds at present: a kind of is to utilize two keys of polyolefin chain end and borine, maleic anhydride (Mulhaupt R et al, Macromol Chem Macromol Symp1991,48/19:317; Shiono T et al, Macromolecules 1993,26:2085) wait reaction, thereby obtain the polyolefine of end group functional.But the functionalization transformation efficiency of this method is not high, and reaction will be carried out after polyolefine forms.Another kind is to add chain-transfer agent, (Fu PF et al, JAm Chem Soc 1998,120:4019 when olefinic polymerization; Kwangmo K et al, Macromolecules 1999,32:981; Xu G et al, J Am Chem Soc 1999,121:6763; Xu G et al, Polym Prepr2000 41:1926) utilizes the chain transfer reaction in the olefinic polymerization to obtain the polyolefine that end group has polar group.But the used chain-transfer agent of this method needs special synthetic usually, and adds chain-transfer agent and also make the catalyzed polymerization decrease in efficiency.In addition, in this way the polyolefinic molecular weight of end group functional of preparation is all lower.More than two class methods all need after olefinic polymerization, handle polymkeric substance, carry out twice separation and purification to polymkeric substance, therefore the step more complicated is not suitable for the large-scale preparation of producing.
After the polyolefinic end of the chain is introduced reactive group, can improve consistency with other material, and from the polyolefine of end group functional, can prepare various segmented copolymers and graft copolymer, in polymer blending, prepare composite all can be widely used, and this will greatly expand polyolefinic range of application, can estimate that the polyolefine of functionalization will have vast market prospect.Therefore, the functional polyolefin of synthesizing new, and develop a kind of polyolefine synthetic method of easy, easy row, be very necessary.
Summary of the invention
A purpose of the present invention is to provide a kind of terminal hydroxy group polypropylene, and this terminal hydroxy group polypropylene has terminal hydroxy group functionality height (〉=0.8), has characteristics such as height isotactic steric configuration, molecular weight adjustable height, narrow molecular weight distribution.
A further object of the present invention is to provide a kind of method simple, can the polyacrylic method of scale operation terminal hydroxy group.
Terminal hydroxy group polypropylene of the present invention is the polypropylene that macromolecular chain one end has an oh group, and its general structure is:
Wherein, the arbitrary integer between n=100～100,000.
The polyacrylic functionality of described terminal hydroxy group is not less than 0.8.
Described polypropylene chains is complete same steric configuration, and polyacrylic molecular weight distribution is 2～5, and polyacrylic molecular weight is 5000～5000000g/mol.
Terminal hydroxy group of the present invention is polyacrylic preparation method carry out according to the following steps:
(1) under inert atmosphere, organic solvent and alkylaluminoxane promotor are joined in the polymerization reactor, 0～100 ℃ was stirred 1～60 minute down; Replace rare gas element with propylene gas then, keeping propylene gas pressure is 0.05～0.2Mpa;
(2) under 0～100 ℃, metallocene catalyst is joined in the solution of step (1) mol ratio of alkylaluminoxane promotor and metallocene catalyst=100: 1～100000: 1, preferred 300: 1～10000: 1; The concentration of metallocene catalyst is 10
-8～10
-3Mol/L, 0～100 ℃ was stirred 1～120 minute down, and propylene gas pressure remains on 0.1～5Mpa in the polymerization process;
(3) with the reaction product of step (2) with oxygen or atmospheric oxidation 1～10 hour, add excessive hydrogen peroxide and M (OH) then
xThe aqueous solution, under 20～150 ℃, be hydrolyzed the reaction 1～40 hour;
(4) with the reaction product of step (3) with excessive 10% acidic alcohol precipitation, filter white solid, with second alcohol and water thorough washing final vacuum drying, obtain the terminal hydroxy group polypropylene.
Described rare gas element is nitrogen or argon gas etc.
Described organic solvent is saturated arene, as: hexane, heptane, benzene,toluene,xylene or their any mixture are preferably toluene.
Described alkylaluminoxane is methylaluminoxane (MAO), ethyl aikyiaiurnirsoxan beta (EAO) or isobutyl aluminium alkoxide (iBAO) etc., wherein preferable methyl aikyiaiurnirsoxan beta.Maintenance Al/Mt mol ratio=100: 1～100000: 1, preferred 300: 1～10000: 1.
Described M (OH)
xMiddle x=1 or 2, M is Li, Na, K, Rb, Mg, Ca, Sr or Ba.
Terminal hydroxy group polypropylene of the present invention and preparation method thereof has following feature:
1. the polyacrylic end of polypropylene chains that is characterised in that of terminal hydroxy group contains a hydroxyl.
2. the polyacrylic preparation method of terminal hydroxy group at first with propylene polymerization at a certain temperature, and then can obtain the polypropylene that end group is a hydroxyl through oxidation and hydrolysis.
3. the polyacrylic preparation method of terminal hydroxy group, the used metallocene catalyst of polymerization is the cyclopentadinyl compound of transition metal such as Ti, Zr, Hf, Co or Nd normally.Described metallocene catalyst is selected from one or more the mixture in the metallocene catalyst with following general formula:
(1)Me
2Si[(2-R
1，4-R
2)C
5H
2]
2ZrCl
2
R
1=tert-Bu, R
2=H; Or
R
1=tert-Bu, R
2=Me; Or
R
1＝i-Pr，R
2＝Me；
(2)Me
2Si(C
5H
5-nR
n)(C
5H
5-nR’
n)ZrCl
2
R
n=2,3,5-Me
3, R ' n=2,4,5-Me
3Or
R
n=2,4-Me
2, R '
n=3,5-Me
2Or
R
n=3-(tert-Bu), R '
n=4-(tert-Bu); Or
R
n＝3-Me，R’
n＝4-Me
n＝1～3
(3)Me
2Si(C
5H
5-nR
n)(C
5H
5-nR’
n)ZrCl
2
R
n=2,4-Me
2, R '
n=3-Me or R '
n=4-Me; Or
R
n=3,4-Me
2, R '
n=3-Me; Or
R
n=3-(tert-Bu), R '
n=3-or 4-Me; Or
R
n=2,3,5-Me
3, R '
n=H; Or
R
n=2,4-Me
2, R '
n=H; Or
R
n=3-(tert-Bu), R '
n=H; Or
R
n＝3-Me，R’
n＝H；
n＝1～3
(4)C
2H
4(3-MeInd)
2ZrCl
2
(5)C
2H
4(5，6-X
2Ind)
2ZrCl
2
X=H, Me or OMe
(6)Me
2C(Ind)
2ZrCl
2
(7)Me
2C(2-t-Bu-Ind)
2ZrCl
2
(8)Ph
2Si(Ind)
2ZrCl
2
(9)(Ph)(Me)Si(2-MeInd)
2ZrCl
2
(10) Me
2Si[2-R-Ind]
2ZrCl
2R=H or Me
(11) Me
2Si[2-R-IndH
4]
2ZrCl
2R=H or Me
(12)Me
2Si[2-R
1-4-R
2-Ind]
2ZrCl
2
R
1=Me, R
2=i-Pr; Or
R
1=Me, R
2=benzo; Or
R
1=H, R
2=benzo; Or
R
1=Me, R
2=1-naphthyl; Or
R
1＝Me，R
2＝Phenyl；
(13)(R
1)(R
2)Si[2-R
3-4-phenyl-Ind]
2ZrCl
2
R
1=R
2=R
3=Me; Or
R
1=R
2=R
3=Phenyl; Or
R
1＝R
2＝Me，R
3＝H；
(14)Me
2Si[2-Me-5-phenyl-Ind]
2ZrCl
2；
Wherein Me is CH
3, Ind is an indenyl, and Ph or phenyl are phenyl, and benzo is the benzo base, and tert-Bu or t-Bu are the tertiary butyl, and naphthyl is a naphthyl, and i-Pr is a sec.-propyl.
The metallocene catalysis agent concentration is 10
-8Mol/L～10
-3Mol/L.
The polyacrylic preparation method of terminal hydroxy group of the present invention at first is to carry out propylene polymerization under certain condition, and direct polymkeric substance to gained carries out oxidation and hydrolysis in the polymerization system then, can obtain the terminal hydroxy group polypropylene.Advantage of the present invention is: 1) need not to add other reactant in olefin polymerization process, can not produce adverse influence to olefinic polymerization; 2) can after polymerization finishes, in polymeric kettle, carry out immediately the functionalization of polymkeric substance, simplify operating process greatly; The ratio height and the adjustable ratio of the polymer end based hydroxyl-containing that 3) obtains; 4) compound with regular structure that can the controlling polymers chain; 5) molecular weight of controlling polymers easily.
Present method can be synthesized the terminal hydroxy group polypropylene easily, and can be to the hydroxy radical content of resulting polymers, molecular weight and distribution thereof, and amylose regularity is controlled.
Description of drawings
Fig. 1. the embodiment of the invention 4 is typical
1H NMR figure.
Fig. 2. the embodiment of the invention 5 is typical
13C NMR figure.
Embodiment
Catalyzer: dimethyl silicon bridge two (2-methyl-4-naphthyl-indenyl) zirconium dichloride
Promotor: methylaluminoxane
Under argon gas atmosphere, the methylaluminoxane promotor of 50mL toluene and 1.8mL1.4mol/L is joined in the polymerization reactor, 30 ℃ were stirred 10 minutes down; Replace argon gas three times with propylene gas then, keeping propylene gas pressure is 0.1Mpa; Under 30 ℃, add 2.5 * 10 then
-6The metallocene catalyst of mol, the mol ratio of methylaluminoxane promotor and metallocene catalyst=1000: 1,30 ℃ were stirred 30 minutes down, and propylene gas pressure remains on 0.1Mpa in the polymerization process; After polyreaction finishes, reactant with dioxygen oxidation 2 hours, is added the aqueous sodium hydroxide solution of 6mL 30% hydrogen peroxide and 20mL0.1g/mL then, reaction 4 hours is hydrolyzed under 50 ℃; Then with reaction product with excessive 10wt% acidic alcohol precipitation, filter white solid, with second alcohol and water thorough washing final vacuum drying, promptly obtain the terminal hydroxy group polypropylene.The polyacrylic constitutional features of reaction conditions and terminal hydroxy group is listed in the table 1.
Catalyzer: dimethyl silicon bridge two (2-methyl-4-naphthyl-indenyl) zirconium dichloride
Promotor: methylaluminoxane
Under argon gas atmosphere, the methylaluminoxane promotor of 50mL toluene and 3.6mL1.4mol/L is joined in the polymerization reactor, 30 ℃ were stirred 10 minutes down; Replace argon gas three times with propylene gas then, keeping propylene gas pressure is 0.1Mpa; Under 30 ℃, add 2.5 * 10 then
-6The metallocene catalyst of mol, the mol ratio of methylaluminoxane promotor and metallocene catalyst=2000: 1,30 ℃ were stirred 30 minutes down, and propylene gas pressure remains on 0.1Mpa in the polymerization process; After polyreaction finishes, reactant with dioxygen oxidation 2 hours, is added the aqueous sodium hydroxide solution of 12mL 30% hydrogen peroxide and 20mL0.2g/mL then, reaction 4 hours is hydrolyzed under 50 ℃; Then with reaction product with excessive 10wt% acidic alcohol precipitation, filter white solid, with second alcohol and water thorough washing final vacuum drying, promptly obtain the terminal hydroxy group polypropylene.The polyacrylic constitutional features of reaction conditions and terminal hydroxy group is listed in the table 1.
Catalyzer: dimethyl silicon bridge two (2-methyl-4-naphthyl-indenyl) zirconium dichloride promotor: methylaluminoxane
Under argon gas atmosphere, the methylaluminoxane promotor of 50mL toluene and 5.4mL1.4mol/L is joined in the polymerization reactor, 30 ℃ were stirred 20 minutes down; Replace argon gas three times with propylene gas then, keeping propylene gas pressure is 0.1Mpa; Under 30 ℃, add 2.5 * 10 then
-6The metallocene catalyst of mol, the mol ratio of methylaluminoxane promotor and metallocene catalyst=3000: 1,30 ℃ were stirred 30 minutes down, and propylene gas pressure remains on 0.1Mpa in the polymerization process; After polyreaction finishes, reactant with dioxygen oxidation 2 hours, is added the aqueous sodium hydroxide solution of 18mL 30% hydrogen peroxide and 30mL0.2g/mL then, reaction 8 hours is hydrolyzed under 50 ℃; Then with reaction product with excessive 10wt% acidic alcohol precipitation, filter white solid, with second alcohol and water thorough washing final vacuum drying, promptly obtain the terminal hydroxy group polypropylene.The polyacrylic constitutional features of reaction conditions and terminal hydroxy group is listed in the table 1.
Catalyzer: dimethyl silicon bridge two (2-methyl-4-naphthyl-indenyl) zirconium dichloride promotor: methylaluminoxane
Under argon gas atmosphere, the methylaluminoxane promotor of 50mL toluene and 9mL1.4mol/L is joined in the polymerization reactor, 30 ℃ were stirred 20 minutes down; Replace argon gas three times with propylene gas then, keeping propylene gas pressure is 0.1Mpa; Under 30 ℃, add 2.5 * 10 then
-6The metallocene catalyst of mol, the mol ratio of methylaluminoxane promotor and metallocene catalyst=5000: 1,30 ℃ were stirred 30 minutes down, and propylene gas pressure remains on 0.1Mpa in the polymerization process; After polyreaction finishes, reactant with dioxygen oxidation 2 hours, is added the aqueous sodium hydroxide solution of 30mL 30% hydrogen peroxide and 50mL0.2g/mL then, reaction 8 hours is hydrolyzed under 50 ℃; Then with reaction product with excessive 10wt% acidic alcohol precipitation, filter white solid, with second alcohol and water thorough washing final vacuum drying, promptly obtain the terminal hydroxy group polypropylene.The polyacrylic constitutional features of reaction conditions and terminal hydroxy group is listed in the table 1.Accompanying drawing 1 be the polyacrylic structure of gained terminal hydroxy group and
1H NMR figure.
Embodiment 5
Catalyzer: dimethyl silicon bridge two (2-methyl-4-naphthyl-indenyl) zirconium dichloride promotor: methylaluminoxane
Under argon gas atmosphere, the methylaluminoxane promotor of 50mL toluene and 18mL1.4mol/L is joined in the polymerization reactor, 30 ℃ were stirred 30 minutes down; Replace argon gas three times with propylene gas then, keeping propylene gas pressure is 0.1Mpa; Under 30 ℃, add 2.5 * 10 then
-6The metallocene catalyst of mol, the mol ratio of methylaluminoxane promotor and metallocene catalyst=10000: 1,30 ℃ were stirred 30 minutes down, and propylene gas pressure remains on 0.1Mpa in the polymerization process; After polyreaction finishes, reactant with dioxygen oxidation 2 hours, is added the aqueous sodium hydroxide solution of 60mL 30% hydrogen peroxide and 100mL0.2g/mL then, reaction 8 hours is hydrolyzed under 50 ℃; Then with reaction product with excessive 10wt% acidic alcohol precipitation, filter white solid, with second alcohol and water thorough washing final vacuum drying, promptly obtain the terminal hydroxy group polypropylene.The polyacrylic constitutional features of reaction conditions and terminal hydroxy group is listed in the table 1.Accompanying drawing 2 be the polyacrylic structure of gained terminal hydroxy group and
13C NMR figure.
Embodiment 6
Catalyzer: dimethyl silicon bridge two (2-methyl-4-naphthyl-indenyl) zirconium dichloride promotor: methylaluminoxane
Under argon gas atmosphere, the methylaluminoxane promotor of 100mL heptane and 9mL1.4mol/L is joined in the polymerization reactor, 30 ℃ were stirred 15 minutes down; Replace argon gas three times with propylene gas then, keeping propylene gas pressure is 0.1Mpa; Under 30 ℃, add 2.5 * 10 then
-6The metallocene catalyst of mol, the mol ratio of methylaluminoxane promotor and metallocene catalyst=5000: 1,30 ℃ were stirred 30 minutes down, and propylene gas pressure remains on 0.1Mpa in the polymerization process; After polyreaction finishes, reactant with dioxygen oxidation 1 hour, is added the aqueous sodium hydroxide solution of 30mL 30% hydrogen peroxide and 50mL0.2g/mL then, reaction 1 hour is hydrolyzed under 50 ℃; Then with reaction product with excessive 10wt% acidic alcohol precipitation, filter white solid, with second alcohol and water thorough washing final vacuum drying, promptly obtain the terminal hydroxy group polypropylene.The polyacrylic constitutional features of reaction conditions and terminal hydroxy group is listed in the table 1.
Embodiment 7
Catalyzer: dimethyl silicon bridge two (2-methyl-4-naphthyl-indenyl) zirconium dichloride promotor: methylaluminoxane
Under argon gas atmosphere, the methylaluminoxane promotor of 100mL heptane and 9mL1.4mol/L is joined in the polymerization reactor, 30 ℃ were stirred 15 minutes down; Replace argon gas three times with propylene gas then, keeping propylene gas pressure is 0.1Mpa; Under 30 ℃, add 2.5 * 10 then
-6The metallocene catalyst of mol, the mol ratio of methylaluminoxane promotor and metallocene catalyst=5000: 1,30 ℃ were stirred 15 minutes down, and propylene gas pressure remains on 0.1Mpa in the polymerization process; After polyreaction finishes, reactant with dioxygen oxidation 3 hours, is added the aqueous sodium hydroxide solution of 30mL 30% hydrogen peroxide and 50mL0.2g/mL then, reaction 5 hours is hydrolyzed under 50 ℃; Then with reaction product with excessive 10wt% acidic alcohol precipitation, filter white solid, with second alcohol and water thorough washing final vacuum drying, promptly obtain the terminal hydroxy group polypropylene.The polyacrylic constitutional features of reaction conditions and terminal hydroxy group is listed in the table 1.
Catalyzer: dimethyl silicon bridge two (2-methyl-4-naphthyl-indenyl) zirconium dichloride promotor: ethyl aikyiaiurnirsoxan beta
Under argon gas atmosphere, the ethyl aluminoxane catalyst of 100mL heptane and 9mL1.4mol/L is joined in the polymerization reactor, 30 ℃ were stirred 15 minutes down; Replace argon gas three times with propylene gas then, keeping propylene gas pressure is 0.1Mpa; Under 30 ℃, add 2.5 * 10 then
-6The metallocene catalyst of mol, the mol ratio of ethyl aluminoxane catalyst and metallocene catalyst=5000: 1,30 ℃ were stirred 15 minutes down, and propylene gas pressure remains on 0.1Mpa in the polymerization process; After polyreaction finishes, reactant with dioxygen oxidation 4 hours, is added the aqueous sodium hydroxide solution of 30mL 30% hydrogen peroxide and 50mL0.2g/mL then, reaction 10 hours is hydrolyzed under 50 ℃; Then with reaction product with excessive 10wt% acidic alcohol precipitation, filter white solid, with second alcohol and water thorough washing final vacuum drying, promptly obtain the terminal hydroxy group polypropylene.The polyacrylic constitutional features of reaction conditions and terminal hydroxy group is listed in the table 1.
Embodiment 9
Catalyzer: dimethyl silicon bridge two (2-methyl-4-naphthyl-indenyl) zirconium dichloride promotor: ethyl aikyiaiurnirsoxan beta
Under argon gas atmosphere, the ethyl aluminoxane catalyst of 100mL heptane and 9mL1.4mol/L is joined in the polymerization reactor, 30 ℃ were stirred 15 minutes down; Replace argon gas three times with propylene gas then, keeping propylene gas pressure is 0.1Mpa; Under 30 ℃, add 2.5 * 10 then
-6The metallocene catalyst of mol, the mol ratio of ethyl aluminoxane catalyst and metallocene catalyst=5000: 1,30 ℃ were stirred 15 minutes down, and propylene gas pressure remains on 0.1Mpa in the polymerization process; After polyreaction finishes, reactant with dioxygen oxidation 6 hours, is added the aqueous sodium hydroxide solution of 30mL 30% hydrogen peroxide and 50mL0.2g/mL then, reaction 20 hours is hydrolyzed under 50 ℃; Then with reaction product with excessive 10wt% acidic alcohol precipitation, filter white solid, with second alcohol and water thorough washing final vacuum drying, promptly obtain the terminal hydroxy group polypropylene.The polyacrylic constitutional features of reaction conditions and terminal hydroxy group is listed in the table 1.
Embodiment 10
Catalyzer: ethyl bridge two indenyl zirconium dichloride promotors: methylaluminoxane
Under argon gas atmosphere, the methylaluminoxane promotor of 250mL heptane and 9mL1.4mol/L is joined in the polymerization reactor, 0 ℃ was stirred 15 minutes down; Replace argon gas three times with propylene gas then, keeping propylene gas pressure is 0.1Mpa; Under 0 ℃, add 2.5 * 10 then
-6The metallocene catalyst of mol, the mol ratio of methylaluminoxane promotor and metallocene catalyst=5000: 1,0 ℃ was stirred 60 minutes down, and propylene gas pressure remains on 0.1Mpa in the polymerization process; After polyreaction finishes, reactant with dioxygen oxidation 2 hours, is added the aqueous sodium hydroxide solution of 6mL 30% hydrogen peroxide and 20mL0.1g/mL then, reaction 2 hours is hydrolyzed under 50 ℃; Then with reaction product with excessive 10wt% acidic alcohol precipitation, filter white solid, with second alcohol and water thorough washing final vacuum drying, promptly obtain the terminal hydroxy group polypropylene.The polyacrylic constitutional features of reaction conditions and terminal hydroxy group is listed in the table 1.
Embodiment 11
Catalyzer: ethyl bridge two indenyl zirconium dichloride promotors: methylaluminoxane
Under argon gas atmosphere, the methylaluminoxane promotor of 250mL heptane and 9mL1.4mol/L is joined in the polymerization reactor, 10 ℃ were stirred 15 minutes down; Replace argon gas three times with propylene gas then, keeping propylene gas pressure is 0.1Mpa; Under 10 ℃, add 2.5 * 10 then
-6The metallocene catalyst of mol, the mol ratio of methylaluminoxane promotor and metallocene catalyst=5000: 1,10 ℃ were stirred 60 minutes down, and propylene gas pressure remains on 0.1Mpa in the polymerization process; After polyreaction finishes, reactant with dioxygen oxidation 2 hours, is added the aqueous sodium hydroxide solution of 6mL 30% hydrogen peroxide and 20mL0.1g/mL then, reaction 2 hours is hydrolyzed under 50 ℃; Then with reaction product with excessive 10wt% acidic alcohol precipitation, filter white solid, with second alcohol and water thorough washing final vacuum drying, promptly obtain the terminal hydroxy group polypropylene.The polyacrylic constitutional features of reaction conditions and terminal hydroxy group is listed in the table 1.
Embodiment 12
Catalyzer: ethyl bridge two indenyl zirconium dichloride promotors: methylaluminoxane
Under argon gas atmosphere, the methylaluminoxane promotor of 250mL toluene and 9mL1.4mol/L is joined in the polymerization reactor, 20 ℃ were stirred 15 minutes down; Replace argon gas three times with propylene gas then, keeping propylene gas pressure is 0.1Mpa; Under 30 ℃, add 2.5 * 10 then
-6The metallocene catalyst of mol, the mol ratio of methylaluminoxane promotor and metallocene catalyst=5000: 1,20 ℃ were stirred 60 minutes down, and propylene gas pressure remains on 0.1Mpa in the polymerization process; After polyreaction finishes, reactant with dioxygen oxidation 2 hours, is added the aqueous sodium hydroxide solution of 30mL 30% hydrogen peroxide and 50mL0.2g/mL then, reaction 4 hours is hydrolyzed under 50 ℃; Then with reaction product with excessive 10wt% acidic alcohol precipitation, filter white solid, with second alcohol and water thorough washing final vacuum drying, promptly obtain the terminal hydroxy group polypropylene.The polyacrylic constitutional features of reaction conditions and terminal hydroxy group is listed in the table 1.
Embodiment 13
Catalyzer: ethyl bridge two indenyl zirconium dichloride promotors: ethyl aikyiaiurnirsoxan beta
Under argon gas atmosphere, the ethyl aluminoxane catalyst of 250mL toluene and 9mL1.4mol/L is joined in the polymerization reactor, 40 ℃ were stirred 10 minutes down; Replace argon gas three times with propylene gas then, keeping propylene gas pressure is 0.1Mpa; Under 40 ℃, add 2.5 * 10 then
-6The metallocene catalyst of mol, the mol ratio of ethyl aluminoxane catalyst and metallocene catalyst=5000: 1,40 ℃ were stirred 60 minutes down, and propylene gas pressure remains on 0.1Mpa in the polymerization process; After polyreaction finishes, reactant with dioxygen oxidation 5 hours, is added the aqueous sodium hydroxide solution of 30mL 30% hydrogen peroxide and 50mL0.2g/mL then, reaction 12 hours is hydrolyzed under 50 ℃; Then with reaction product with excessive 10wt% acidic alcohol precipitation, filter white solid, with second alcohol and water thorough washing final vacuum drying, promptly obtain the terminal hydroxy group polypropylene.The polyacrylic constitutional features of reaction conditions and terminal hydroxy group is listed in the table 1.
Embodiment 14
Catalyzer: ethyl bridge two indenyl zirconium dichloride promotors: isobutyl aluminium alkoxide
Under argon gas atmosphere, the isobutyl aluminium alkoxide promotor of 250mL toluene and 9mL1.4mol/L is joined in the polymerization reactor, 60 ℃ were stirred 10 minutes down; Replace argon gas three times with propylene gas then, keeping propylene gas pressure is 0.1Mpa; Under 60 ℃, add 2.5 * 10 then
-6The metallocene catalyst of mol, the mol ratio of isobutyl aluminium alkoxide promotor and metallocene catalyst=5000: 1,60 ℃ were stirred 60 minutes down, and propylene gas pressure remains on 0.1Mpa in the polymerization process; After polyreaction finishes, reactant with dioxygen oxidation 5 hours, is added the aqueous sodium hydroxide solution of 30mL 30% hydrogen peroxide and 50mL0.2g/mL then, reaction 12 hours is hydrolyzed under 60 ℃; Then with reaction product with excessive 10wt% acidic alcohol precipitation, filter white solid, with second alcohol and water thorough washing final vacuum drying, promptly obtain the terminal hydroxy group polypropylene.The polyacrylic constitutional features of reaction conditions and terminal hydroxy group is listed in the table 1.
Embodiment 15
Catalyzer: ethyl bridge two indenyl zirconium dichloride promotors: methylaluminoxane
Under argon gas atmosphere, the methylaluminoxane promotor of 250mL toluene and 9mL1.4mol/L is joined in the polymerization reactor, 80 ℃ were stirred 10 minutes down; Replace argon gas three times with propylene gas then, keeping propylene gas pressure is 0.1Mpa; Under 80 ℃, add 2.5 * 10 then
-6The metallocene catalyst of mol, the mol ratio of methylaluminoxane promotor and metallocene catalyst=5000: 1,80 ℃ were stirred 60 minutes down, and propylene gas pressure remains on 0.1Mpa in the polymerization process; After polyreaction finishes, reactant with dioxygen oxidation 5 hours, is added the aqueous sodium hydroxide solution of 30mL 30% hydrogen peroxide and 50mL0.2g/mL then, reaction 12 hours is hydrolyzed under 80 ℃; Then with reaction product with excessive 10wt% acidic alcohol precipitation, filter white solid, with second alcohol and water thorough washing final vacuum drying, promptly obtain the terminal hydroxy group polypropylene.The polyacrylic constitutional features of reaction conditions and terminal hydroxy group is listed in the table 1.
Embodiment 16
Catalyzer: dimethyl silicon bridge two (the 2-tertiary butyl-4-methyl-cyclopentadienyl) zirconium dichloride promotor: ethyl aikyiaiurnirsoxan beta
Under argon gas atmosphere, the ethyl aluminoxane catalyst of 50mL toluene and 5.4mL1.4mol/L is joined in the polymerization reactor, 0 ℃ was stirred 20 minutes down; Replace argon gas three times with propylene gas then, keeping propylene gas pressure is 0.1Mpa; Under 0 ℃, add 5 * 10 then
-6The metallocene catalyst of mol, the mol ratio of ethyl aluminoxane catalyst and metallocene catalyst=1500: 1,0 ℃ was stirred 10 minutes down, and propylene gas pressure remains on 0.1Mpa in the polymerization process; After polyreaction finishes, reactant with dioxygen oxidation 2 hours, is added the aqueous sodium hydroxide solution of 9mL 30% hydrogen peroxide and 30mL0.1g/mL then, reaction 6 hours is hydrolyzed under 50 ℃; Then with reaction product with excessive 10wt% acidic alcohol precipitation, filter white solid, with second alcohol and water thorough washing final vacuum drying, promptly obtain the terminal hydroxy group polypropylene.The polyacrylic constitutional features of reaction conditions and terminal hydroxy group is listed in the table 1.
Embodiment 17
Catalyzer: dimethyl silicon bridge two (the 2-tertiary butyl-4-methyl-cyclopentadienyl) zirconium dichloride promotor: isobutyl aluminium alkoxide
Under argon gas atmosphere, the isobutyl aluminium alkoxide promotor of 50mL toluene and 5.4mL1.4mol/L is joined in the polymerization reactor, 10 ℃ were stirred 20 minutes down; Replace argon gas three times with propylene gas then, keeping propylene gas pressure is 0.1Mpa; Under 10 ℃, add 5 * 10 then
-6The metallocene catalyst of mol, the mol ratio of isobutyl aluminium alkoxide promotor and metallocene catalyst=1500: 1,30 ℃ were stirred 10 minutes down, and propylene gas pressure remains on 0.1Mpa in the polymerization process; After polyreaction finishes, reactant with dioxygen oxidation 2 hours, is added the aqueous sodium hydroxide solution of 9mL 30% hydrogen peroxide and 30mL0.1g/mL then, reaction 6 hours is hydrolyzed under 50 ℃; Then with reaction product with excessive 10wt% acidic alcohol precipitation, filter white solid, with second alcohol and water thorough washing final vacuum drying, promptly obtain the terminal hydroxy group polypropylene.The polyacrylic constitutional features of reaction conditions and terminal hydroxy group is listed in the table 1.
Embodiment 18
Catalyzer: dimethyl silicon bridge two (the 2-tertiary butyl-4-methyl-cyclopentadienyl) zirconium dichloride promotor: methylaluminoxane
Under argon gas atmosphere, the methylaluminoxane promotor of 50mL toluene and 5.4mL1.4mol/L is joined in the polymerization reactor, 30 ℃ were stirred 10 minutes down; Replace argon gas three times with propylene gas then, keeping propylene gas pressure is 0.1Mpa; Under 30 ℃, add 2.5 * 10 then
-6The metallocene catalyst of mol, the mol ratio of methylaluminoxane promotor and metallocene catalyst=1500: 1,30 ℃ were stirred 10 minutes down, and propylene gas pressure remains on 0.1Mpa in the polymerization process; After polyreaction finishes, reactant with dioxygen oxidation 2 hours, is added the aqueous sodium hydroxide solution of 9mL 30% hydrogen peroxide and 30mL0.1g/mL then, reaction 6 hours is hydrolyzed under 50 ℃; Then with reaction product with excessive 10wt% acidic alcohol precipitation, filter white solid, with second alcohol and water thorough washing final vacuum drying, promptly obtain the terminal hydroxy group polypropylene.The polyacrylic constitutional features of reaction conditions and terminal hydroxy group is listed in the table 1.
Embodiment 19
Catalyzer: dimethyl silicon bridge two (the 2-tertiary butyl-4-methyl-cyclopentadienyl) zirconium dichloride promotor: methylaluminoxane
Under argon gas atmosphere, the methylaluminoxane promotor of 50mL toluene and 2.7mL1.4mol/L is joined in the polymerization reactor, 40 ℃ were stirred 10 minutes down; Replace argon gas three times with propylene gas then, keeping propylene gas pressure is 0.1Mpa; Under 40 ℃, add 2.5 * 10 then
-6The metallocene catalyst of mol, the mol ratio of methylaluminoxane promotor and metallocene catalyst=1500: 1,40 ℃ were stirred 20 minutes down, and propylene gas pressure remains on 0.1Mpa in the polymerization process; After polyreaction finishes, reactant with dioxygen oxidation 2 hours, is added the aqueous sodium hydroxide solution of 9mL 30% hydrogen peroxide and 30mL0.1g/mL then, reaction 10 hours is hydrolyzed under 50 ℃; Then with reaction product with excessive 10wt% acidic alcohol precipitation, filter white solid, with second alcohol and water thorough washing final vacuum drying, promptly obtain the terminal hydroxy group polypropylene.The polyacrylic constitutional features of reaction conditions and terminal hydroxy group is listed in the table 1.
Catalyzer: dimethyl silicon bridge two (the 2-tertiary butyl-4-methyl-cyclopentadienyl) zirconium dichloride
Promotor: methylaluminoxane
Under argon gas atmosphere, the methylaluminoxane promotor of 50mL toluene and 2.7mL1.4mol/L is joined in the polymerization reactor, 60 ℃ were stirred 10 minutes down; Replace argon gas three times with propylene gas then, keeping propylene gas pressure is 0.1Mpa; Under 60 ℃, add 2.5 * 10 then
-6The metallocene catalyst of mol, the mol ratio of methylaluminoxane promotor and metallocene catalyst=1500: 1,60 ℃ were stirred 20 minutes down, and propylene gas pressure remains on 0.1Mpa in the polymerization process; After polyreaction finishes, reactant with dioxygen oxidation 2 hours, is added the aqueous sodium hydroxide solution of 9mL 30% hydrogen peroxide and 30mL0.1g/mL then, reaction 10 hours is hydrolyzed under 60 ℃; Then with reaction product with excessive 10wt% acidic alcohol precipitation, filter white solid, with second alcohol and water thorough washing final vacuum drying, promptly obtain the terminal hydroxy group polypropylene.The polyacrylic constitutional features of reaction conditions and terminal hydroxy group is listed in the table 1.
Embodiment 21
Catalyzer: dimethyl silicon bridge two (the 2-tertiary butyl-4-methyl-cyclopentadienyl) zirconium dichloride
Promotor: methylaluminoxane
Under nitrogen atmosphere, the methylaluminoxane promotor of 50mL toluene and 2.7mL1.4mol/L is joined in the polymerization reactor, 80 ℃ were stirred 10 minutes down; Replace nitrogen three times with propylene gas then, keeping propylene gas pressure is 0.1Mpa; Under 80 ℃, add 2.5 * 10 then
-6The metallocene catalyst of mol, the mol ratio of methylaluminoxane promotor and metallocene catalyst=1500: 1,80 ℃ were stirred 20 minutes down, and propylene gas pressure remains on 0.1Mpa in the polymerization process; After polyreaction finishes, reactant with dioxygen oxidation 2 hours, is added the aqueous sodium hydroxide solution of 9mL 30% hydrogen peroxide and 30mL0.1g/mL then, reaction 10 hours is hydrolyzed under 80 ℃; Then with reaction product with excessive 10wt% acidic alcohol precipitation, filter white solid, with second alcohol and water thorough washing final vacuum drying, promptly obtain the terminal hydroxy group polypropylene.The polyacrylic constitutional features of reaction conditions and terminal hydroxy group is listed in the table 1.
Embodiment 22
Catalyzer: dimethyl silicon bridge two (2-methyl-4-phenyl-indenyl) zirconium dichloride
Promotor: methylaluminoxane
Under nitrogen atmosphere, the methylaluminoxane promotor of 500mL toluene and 1mL1.4mol/L is joined in the polymerization reactor, 30 ℃ were stirred 30 minutes down; Replace nitrogen three times with propylene gas then, keeping propylene gas pressure is 0.1Mpa; Under 30 ℃, add 2.5 * 10 then
-6The metallocene catalyst of mol, the mol ratio of methylaluminoxane promotor and metallocene catalyst=500: 1,30 ℃ were stirred 120 minutes down, and propylene gas pressure remains on 0.2Mpa in the polymerization process; After polyreaction finishes, reactant with dioxygen oxidation 2 hours, is added the aqueous sodium hydroxide solution of 10mL 30% hydrogen peroxide and 10mL0.1g/mL then, reaction 20 hours is hydrolyzed under 50 ℃; Then with reaction product with excessive 10wt% acidic alcohol precipitation, filter white solid, with second alcohol and water thorough washing final vacuum drying, promptly obtain the terminal hydroxy group polypropylene.The polyacrylic constitutional features of reaction conditions and terminal hydroxy group is listed in the table 1.
Embodiment 23
Catalyzer: dimethyl silicon bridge two (2-methyl-4-phenyl-indenyl) zirconium dichloride promotor: methylaluminoxane
Under nitrogen atmosphere, the methylaluminoxane promotor of 500mL toluene and 1mL1.4mol/L is joined in the polymerization reactor, 40 ℃ were stirred 30 minutes down; Replace nitrogen three times with propylene gas then, keeping propylene gas pressure is 0.1Mpa; Under 40 ℃, add 2.5 * 10 then
-6The metallocene catalyst of mol, the mol ratio of methylaluminoxane promotor and metallocene catalyst=500: 1,40 ℃ were stirred 120 minutes down, and propylene gas pressure remains on 0.4Mpa in the polymerization process; After polyreaction finishes, reactant with dioxygen oxidation 2 hours, is added the aqueous sodium hydroxide solution of 10mL 30% hydrogen peroxide and 10mL0.1g/mL then, reaction 20 hours is hydrolyzed under 50 ℃; Then with reaction product with excessive 10wt% acidic alcohol precipitation, filter white solid, with second alcohol and water thorough washing final vacuum drying, promptly obtain the terminal hydroxy group polypropylene.The polyacrylic constitutional features of reaction conditions and terminal hydroxy group is listed in the table 1.
Embodiment 24
Catalyzer: dimethyl silicon bridge two (2-methyl-4-phenyl-indenyl) zirconium dichloride promotor: methylaluminoxane
Under nitrogen atmosphere, the methylaluminoxane promotor of 500mL toluene and 1mL1.4mol/L is joined in the polymerization reactor, 60 ℃ were stirred 30 minutes down; Replace nitrogen three times with propylene gas then, keeping propylene gas pressure is 0.1Mpa; Under 60 ℃, add 2.5 * 10 then
-6The metallocene catalyst of mol, the mol ratio of methylaluminoxane promotor and metallocene catalyst=500: 1,60 ℃ were stirred 80 minutes down, and propylene gas pressure remains on 0.5Mpa in the polymerization process; After polyreaction finishes, reactant with dioxygen oxidation 4 hours, is added the aqueous sodium hydroxide solution of 10mL 30% hydrogen peroxide and 10mL0.1g/mL then, reaction 20 hours is hydrolyzed under 60 ℃; Then with reaction product with excessive 10wt% acidic alcohol precipitation, filter white solid, with second alcohol and water thorough washing final vacuum drying, promptly obtain the terminal hydroxy group polypropylene.The polyacrylic constitutional features of reaction conditions and terminal hydroxy group is listed in the table 1.
Embodiment 25
Catalyzer: dimethyl silicon bridge two (2-methyl-4-phenyl-indenyl) zirconium dichloride promotor: methylaluminoxane
Under nitrogen atmosphere, the methylaluminoxane promotor of 500mL toluene and 1mL1.4mol/L is joined in the polymerization reactor, 80 ℃ were stirred 30 minutes down; Replace nitrogen three times with propylene gas then, keeping propylene gas pressure is 0.1Mpa; Under 80 ℃, add 2.5 * 10 then
-6The metallocene catalyst of mol, the mol ratio of methylaluminoxane promotor and metallocene catalyst=500: 1,80 ℃ were stirred 60 minutes down, and propylene gas pressure remains on 0.7Mpa in the polymerization process; After polyreaction finishes, reactant with dioxygen oxidation 4 hours, is added the aqueous sodium hydroxide solution of 10mL 30% hydrogen peroxide and 10mL0.1g/mL then, reaction 20 hours is hydrolyzed under 80 ℃; Then with reaction product with excessive 10wt% acidic alcohol precipitation, filter white solid, with second alcohol and water thorough washing final vacuum drying, promptly obtain the terminal hydroxy group polypropylene.The polyacrylic constitutional features of reaction conditions and terminal hydroxy group is listed in the table 1.
Embodiment 26
Catalyzer: dimethyl silicon bridge two (2-methyl-4-naphthyl-indenyl) zirconium dichloride
Dimethyl silicon bridge two (2-methyl-4-phenyl-indenyl) zirconium dichloride promotor: methylaluminoxane
Under nitrogen atmosphere, the methylaluminoxane promotor of 500mL toluene and 1mL1.4mol/L is joined in the polymerization reactor, 50 ℃ were stirred 30 minutes down; Replace nitrogen three times with propylene gas then, keeping propylene gas pressure is 0.1Mpa; Under 50 ℃, add 5 * 10 then
-6The metallocene catalyst of mol (mol ratio of two kinds of metallocene catalysts is 1: 1), the mol ratio of methylaluminoxane promotor and metallocene catalyst=250: 1,50 ℃ were stirred 60 minutes down, and propylene gas pressure remains on 0.3Mpa in the polymerization process; After polyreaction finishes, reactant with atmospheric oxidation 2 hours, is added the aqueous sodium hydroxide solution of 10mL 30% hydrogen peroxide and 10mL0.1g/mL then, reaction 20 hours is hydrolyzed under 50 ℃; Then with reaction product with excessive 10wt% acidic alcohol precipitation, filter white solid, with second alcohol and water thorough washing final vacuum drying, promptly obtain the terminal hydroxy group polypropylene.The polyacrylic constitutional features of reaction conditions and terminal hydroxy group is listed in the table 1.
Embodiment 27
Catalyzer: dimethyl silicon bridge two (2-methyl-4-naphthyl-indenyl) zirconium dichloride
Ethyl bridge two indenyl zirconium dichloride promotors: methylaluminoxane
Under nitrogen atmosphere, the methylaluminoxane promotor of 500mL toluene and 1mL1.4mol/L is joined in the polymerization reactor, 50 ℃ were stirred 30 minutes down; Replace nitrogen three times with propylene gas then, keeping propylene gas pressure is 0.1Mpa; Under 50 ℃, add 2.5 * 10 then
-6The metallocene catalyst of mol (mol ratio of two kinds of metallocene catalysts is 1: 1), the mol ratio of methylaluminoxane promotor and metallocene catalyst=500: 1,50 ℃ were stirred 60 minutes down, and propylene gas pressure remains on 0.3Mpa in the polymerization process; After polyreaction finishes, reactant with atmospheric oxidation 2 hours, is added the aqueous sodium hydroxide solution of 10mL 30% hydrogen peroxide and 10mL0.1g/mL then, reaction 20 hours is hydrolyzed under 50 ℃; Then with reaction product with excessive 10wt% acidic alcohol precipitation, filter white solid, with second alcohol and water thorough washing final vacuum drying, promptly obtain the terminal hydroxy group polypropylene.The polyacrylic constitutional features of reaction conditions and terminal hydroxy group is listed in the table 1.
Embodiment 28
Catalyzer: ethyl bridge two indenyl zirconium dichlorides
Dimethyl silicon bridge two (the 2-tertiary butyl-4-methyl-cyclopentadienyl) zirconium dichloride
Promotor: methylaluminoxane
Under nitrogen atmosphere, the methylaluminoxane promotor of 500mL toluene and 1mL1.4mol/L is joined in the polymerization reactor, 50 ℃ were stirred 30 minutes down; Replace nitrogen three times with propylene gas then, keeping propylene gas pressure is 0.1Mpa; Under 50 ℃, add 2.5 * 10 then
-6The metallocene catalyst of mol (mol ratio of two kinds of metallocene catalysts is 1: 1), the mol ratio of methylaluminoxane promotor and metallocene catalyst=500: 1,50 ℃ were stirred 60 minutes down, and propylene gas pressure remains on 0.5Mpa in the polymerization process; After polyreaction finishes, reactant with atmospheric oxidation 2 hours, is added the aqueous sodium hydroxide solution of 10mL 30% hydrogen peroxide and 10mL0.1g/mL then, reaction 20 hours is hydrolyzed under 50 ℃; Then with reaction product with excessive 10wt% acidic alcohol precipitation, filter white solid, with second alcohol and water thorough washing final vacuum drying, promptly obtain the terminal hydroxy group polypropylene.The polyacrylic constitutional features of reaction conditions and terminal hydroxy group is listed in the table 1.
Table 1 embodiment reaction conditions and polymer architecture feature
| The embodiment numbering | The catalyzer promotor | Catalyst concn (mol/L) | Al/Zr | Propylene pressure Mpa | Temperature of reaction (℃) | Reaction times (branch) | Oxidization time (hour) | Hydrolysis time (hour) | Molecular weight (g/mol) | Polymerization degree n | Molecular weight distribution | Fusing point (℃) | The terminal hydroxy group functionality |
| 1 | 1/MAO | 5.0×10 -5 | 1000 | 0.1 | 30 | 30 | 2 | 4 | 131000 | 3120 | 2.58 | 157.5 | 0.76 |
| 2 | 1/MAO | 5.0×10 -5 | 2000 | 0.1 | 30 | 30 | 2 | 4 | 52000 | 1240 | 3.07 | 153.0 | 0.77 |
| 3 | 1/MAO | 5.0×10 -5 | 3000 | 0.1 | 30 | 30 | 2 | 8 | 40000 | 950 | 3.54 | 154.7 | 0.88 |
| 4 | 1/MAO | 5.0×10 -5 | 5000 | 0.1 | 30 | 30 | 2 | 8 | 34000 | 810 | 3.78 | 152.7 | 0.85 |
| 5 | 1/MAO | 5.0×10 -5 | 10000 | 0.1 | 30 | 30 | 2 | 8 | 22000 | 520 | 3.70 | 151.7 | 0.86 |
| 6 | 1/MAO | 2.5×10 -5 | 5000 | 0.1 | 30 | 30 | 1 | 1 | 29000 | 690 | 3.23 | 152.1 | 0.87 |
| 7 | 1/MAO | 2.5×10 -5 | 5000 | 0.1 | 30 | 15 | 3 | 5 | 24000 | 570 | 3.75 | 151.9 | 0.86 |
| 8 | 1/EAO | 2.5×10 -5 | 5000 | 0.1 | 30 | 15 | 4 | 10 | 29000 | 690 | 2.93 | 152.5 | 0.93 |
| 9 | 1/EAO | 2.5×10 -5 | 5000 | 0.1 | 30 | 15 | 6 | 20 | 28000 | 670 | 3.50 | 152.8 | 0.84 |
| 10 | 2/MAO | 1.0×10 -5 | 5000 | 0.1 | 0 | 60 | 2 | 2 | 457000 | 10880 | 2.10 | 162.3 | 1.00 |
| 11 | 2/MAO | 1.0×10 -5 | 5000 | 0.1 | 10 | 60 | 2 | 2 | 119000 | 2830 | 2.23 | 160.2 | 0.93 |
| 12 | 2/MAO | 1.0×10 -5 | 5000 | 0.1 | 20 | 60 | 2 | 4 | 44000 | 1050 | 2.63 | 158.0 | 0.94 |
| 13 | 2/EAO | 1.0×10 -5 | 5000 | 0.1 | 40 | 60 | 5 | 12 | 20000 | 480 | 2.94 | 152.1 | 0.84 |
| 14 | 2/iBAO | 1.0×10 -5 | 5000 | 0.1 | 60 | 60 | 5 | 12 | 14000 | 330 | 3.47 | 151.6 | 0.84 |
| 15 | 2/MAO | 1.0×10 -5 | 5000 | 0.1 | 80 | 60 | 5 | 12 | 15000 | 360 | 3.85 | 151.8 | 0.39 |
| 16 | 3/EAO | 1.0×10 -4 | 1500 | 0.1 | 0 | 10 | 2 | 6 | 321000 | 7640 | 2.57 | 159.3 | 1.00 |
| 17 | 3/iBAO | 1.0×10 -4 | 1500 | 0.1 | 10 | 10 | 2 | 6 | 315000 | 7500 | 2.94 | 160.5 | 1.00 |
| 18 | 3/MAO | 1.0×10 -4 | 1500 | 0.1 | 30 | 10 | 2 | 6 | 79000 | 1880 | 3.87 | 157.6 | 0.74 |
| 19 | 3/MAO | 5.0×10 -5 | 1500 | 0.1 | 40 | 20 | 2 | 10 | 66000 | 1570 | 3.71 | 156.5 | 0.74 |
| 20 | 3/MAO | 5.0×10 -5 | 1500 | 0.1 | 60 | 20 | 2 | 10 | 20000 | 480 | 3.92 | 147.8 | 0.66 |
| 21 | 3/MAO | 5.0×10 -5 | 1500 | 0.1 | 80 | 20 | 2 | 10 | 15000 | 360 | 3.79 | 144.5 | 0.58 |
| The embodiment numbering | The catalyzer promotor | Catalyst concn (mol/L) | Al/Zr | Propylene pressure Mpa | Temperature of reaction (℃) | Reaction times (branch) | Oxidization time (hour) | Hydrolysis time (hour) | Molecular weight (g/mol) | Polymerization degree n | Molecular weight distribution | Fusing point (℃) | The terminal hydroxy group functionality |
| 22 | 4/MA0 | 5.0×10 -6 | 500 | 0.2 | 30 | 120 | 2 | 20 | 368000 | 8760 | 2.51 | 154.8 | 0.57 |
| 23 | 4/MAO | 5.0×10 -6 | 500 | 0.4 | 40 | 120 | 2 | 20 | 210000 | 5000 | 2.38 | 159.3 | 1.00 |
| 24 | 4/MAO | 5.0×10 -6 | 500 | 0.5 | 60 | 80 | 4 | 20 | 323000 | 7690 | 2.69 | 160.1 | 0.46 |
| 25 | 4/MAO | 5.0×10 -6 | 500 | 0.7 | 80 | 60 | 4 | 20 | 540000 | 12860 | 2.56 | 161.3 | 0.51 |
| 26 | 1，4/MAO | 1.0×10 -5 | 250 | 0.3 | 50 | 60 | 2 | 20 | 742000 | 17670 | 3.89 | 159.5 | 0.87 |
| 27 | 1，2/MAO | 5.0×10 -6 | 500 | 0.3 | 50 | 60 | 2 | 20 | 466000 | 11100 | 2.95 | 160.2 | 0.85 |
| 28 | 2，3/MAO | 5.0×10 -6 | 500 | 0.5 | 50 | 60 | 2 | 20 | 928000 | 22100 | 3.05 | 161.2 | 0.90 |
Annotate: catalyzer: 1=dimethyl silicon bridge two (2-methyl-4-naphthyl-indenyl) zirconium dichloride
2=ethyl bridge two indenyl zirconium dichlorides
3=dimethyl silicon bridge two (the 2-tertiary butyl-4-methyl-cyclopentadienyl) zirconium dichloride
4=dimethyl silicon bridge two (2-methyl-4-phenyl-indenyl) zirconium dichloride
Promotor: MAO=methylaluminoxane
EAO=ethyl aikyiaiurnirsoxan beta
The iBAO=isobutyl aluminium alkoxide
Claims (7)
1. polyacrylic preparation method of terminal hydroxy group, it is characterized in that: this method is carried out according to the following steps:
(1) under inert atmosphere, organic solvent and alkylaluminoxane promotor are joined in the polymerization reactor, 0～100 ℃ is stirred down; Replace rare gas element with propylene gas then, keeping propylene gas pressure is 0.05～0.2Mpa;
(2) metallocene catalyst is joined in the solution of step (1), the mol ratio of alkylaluminoxane promotor and metallocene catalyst is 100: 1～100000: 1; The ratio of metallocene catalyst and organic solvent is 10
-8～10
-3Mol/L, 0～100 ℃ of following polymerization, propylene gas pressure remains on 0.1～5Mpa in the polymerization process;
(3) with the reaction product of step (2) with oxygen or atmospheric oxidation, add excessive hydrogen peroxide and M (OH) then
xThe aqueous solution, reaction is hydrolyzed under 20～150 ℃;
(4) with the reaction product of step (3) with excessive acidic alcohol precipitation, filter white solid, with second alcohol and water thorough washing final vacuum drying, obtain the terminal hydroxy group polypropylene;
Described M (OH)
xMiddle x=1 or 2; M is Li, Na, K, Rb, Mg, Ca, Sr or Ba.
2. method according to claim 1 is characterized in that: described stirring is 1～60 minute.
3. method according to claim 1 is characterized in that: described hydrolysis reaction 1～40 hour.
4. method according to claim 1 is characterized in that: described organic solvent is hexane, heptane, benzene,toluene,xylene or their any mixture.
5. method according to claim 1 is characterized in that: described alkylaluminoxane is methylaluminoxane, ethyl aikyiaiurnirsoxan beta or isobutyl aluminium alkoxide.
6. method according to claim 1 is characterized in that: described metallocene catalysis agent concentration is 10
-8～10
-3Mol/L.
7. according to claim 1 or 6 described methods, it is characterized in that: described metallocene catalyst is selected from one or more the mixture in the metallocene catalyst with following general formula:
(1)Me
2Si[(2-R
1，4-R
2)C
5H
2]
2ZrCl
2
R
1=tert-Bu, R
2=H; Or
R
1=tert-Bu, R
2=Me; Or
R
1＝i-Pr，R
2＝Me；
(2)Me
2Si(C
5H
5-nR
n)(C
5H
5-nR’
n)ZrCl
2
R
n=2,3,5-Me
3, R ' n=2,4,5-Me
3Or
R
n=2,4-Me
2, R ' n=3,5-Me
2Or
R
n=3-(tert-Bu), R '
n=4-(tert-Bu); Or
R
n＝3-Me，R’
n＝4-Me
n＝1～3
(3)Me
2Si(C
5H
5-nR
n)(C
5H
5-nR’
n)ZrCl
2
R
n=2,4-Me
2, R '
n=3-Me or R '
n=4-Me; Or
R
n=3,4-Me
2, R '
n=3-Me; Or
R
n=3-(tert-Bu), R '
n=3-or 4-Me; Or
R
n=2,3,5-Me
3, R '
n=H; Or
R
n=2,4-Me
2, R '
n=H; Or
R
n=3-(tert-Bu), R '
n=H; Or
R
n＝3-Me，R’
n＝H；
n＝1～3
(4)C
2H
4(3-MeInd)
2ZrCl
2
(5)C
2H
4(5，6-X
2Ind)
2ZrCl
2
X=H, Me or OMe
(6)Me
2C(Ind)
2ZrCl
2
(7)Me
2C(2-t-Bu-Ind)
2ZrCl
2
(8)Ph
2Si(Ind)
2ZrCl
2
(9)(Ph)(Me)Si(2-MeInd)
2ZrCl
2
(10) Me
2Si[2-R-Ind]
2ZrCl
2R=H or Me
(11) Me
2Si[2-R-IndH
4]
2ZrCl
2R=H or Me
(12)Me
2Si[2-R
1-4-R
2-Ind]
2ZrCl
2
R
1=Me, R
2=i-Pr; Or
R
1=Me, R
2=benzo; Or
R
1=H, R
2=benzo; Or
R
1=Me, R
2=1-naphthyl; Or
R
1＝Me，R
2＝Phenyl；
(13)(R
1)(R
2)Si[2-R
3-4-phenyl-Ind]
2ZrCl
2
R
1=R
2=R
3=Me; Or
R
1=R
2=R
3=Phenyl; Or
R
1＝R
2＝Me，R
3＝H；
(14)Me
2Si[2-Me-5-phenyl-Ind]
2ZrCl
2；
Wherein Me is CH
3, Ind is an indenyl, and Ph or phenyl are phenyl, and benzo is the benzo base, and tert-Bu or t-Bu are the tertiary butyl, and naphthyl is a naphthyl, and i-Pr is a sec.-propyl.
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| CN103214605B (en) * | 2013-04-17 | 2015-09-02 | 浙江大学 | Isotatic polypropylene of a kind of terminal hydroxy group functionalization and preparation method thereof |
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| JPH0686484B2 (en) * | 1986-10-31 | 1994-11-02 | 東燃株式会社 | End-modified propylene polymer |
| JPH11228626A (en) * | 1998-02-09 | 1999-08-24 | Tonen Corp | Production of modified polypropylene |
| CN1392886A (en) * | 2000-09-12 | 2003-01-22 | 三井化学株式会社 | Branched polyolefin, process for producing the same, and thermoplastic resin composition containing branched polyolefin |
| CN1495209A (en) * | 2002-08-30 | 2004-05-12 | ������ѧ��ʽ���� | Polyolefine macromonomer, graftmer obtained by utilizing polyolefine macromonomer and its application |
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