CN1209389C - Syndiotactic polystyrene sythesizing 2-hydroxy benzophenone titanium catalyst and its preparing method - Google Patents
Syndiotactic polystyrene sythesizing 2-hydroxy benzophenone titanium catalyst and its preparing method Download PDFInfo
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- CN1209389C CN1209389C CN 03130263 CN03130263A CN1209389C CN 1209389 C CN1209389 C CN 1209389C CN 03130263 CN03130263 CN 03130263 CN 03130263 A CN03130263 A CN 03130263A CN 1209389 C CN1209389 C CN 1209389C
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Abstract
The present invention relates to catalysts in the class of 2-hydroxy benzophenone titanium for synthesizing syndiotactic polystyrene and a preparing method thereof, which belongs to non cyclopentadienyl catalysts for synthesizing syndiotactic polystyrene. The catalysts solve the problem of low molecular weight of the current non cyclopentadienyl catalysts for styrene syndiotactic polymerization; the catalysts in the class of 2-hydroxy benzophenone titanium are provided. The catalysts comprise cocatalysts and main catalysts, wherein the cocatalysts are aluminum alkyl alkane oxides; the main catalysts are the chloride of 2-hydroxy benzophenone titanium, alkoxyl group compounds and phenoxy group or substituted benzene oxo-compounds; the molar ratio is from 2000:1 to 100:1. The catalytic activity of the catalysts is 1*10<4> to 1*10<6> gPS/molTi. h; the catalytic activity can be kept constant for two hours; the raw material for production is cheap; the reaction can be carried out at normal temperature; the production cost is low. When the catalysts are used for synthesizing syndiotactic polystyrene, the technique is convenient, the control is easy, and the molecular weight of obtained polymers is 15 to 30 ten thousands. The catalysts of the present invention promote the industrialization process of the syndiotactic polystyrene.
Description
Technical field
The invention belongs to non cyclopentadienyl catalyst of a kind of synthesis of syndiotactic polystyrene and preparation method thereof, particularly a kind ofly make syndiotactic polystyrene have higher molecular weight, Primary Catalysts is that titaniferous 2-hydroxyl benzophenone title complex, promotor are the catalyzer and the preparation method of alkylaluminoxane.
Technical background
Syndiotactic polystyrene (sPS) is the new type polyolefin material with applications well prospect and important value.1986, Japan goes out Optical Chemical Company and has at first successfully developed novel syndiotactic polystyrene (sPS) (Macromolecues with metallocene catalyst, 1986,19:2464), it has the fusing point height, crystallization velocity is fast, Young's modulus is high, insulation and good solubility-resistence can be good etc. characteristics, almost the Application Areas of all engineering plastics such as PET, PBT, PA, PPS can be used sPS, such as at aspects such as medicine equipment, magneticthin film and electrical insulating film, electrical and electronic component, trolley parts.But, the production of syndiotactic polystyrene (sPS), perfect marketization not as yet so far, its key point is a catalyzer, changes catalyzer and just can obtain specified property and polymerization product ad hoc structure.Therefore, catalyzer just becomes the core and the key of polyolefin industry development.
About synthesis of syndiotactic polymerizing styrene catalyzer, more with the metallocene catalyst report, as Macromol.Chem., Macromol.Symp., 1993,66:203 has reported two (the 6-tertiary butyls-4-methylphenoxy titanium dichloride/MAO synthesis of syndiotactic polystyrene of sulphur bridge.Industrial employing metallocene catalyst is a Primary Catalysts polymerization syndiotactic polystyrene.But metallocene catalyst is synthetic complicated, the synthesis condition harshness, to-20 ℃ of reactions down, need keep low temperature in room temperature with liquid nitrogen, wayward on the technology, and the catalyst activity time length is short, half hour,, catalytic activity just began to reduce, and thermostability is also relatively poor, and promotor MAO consumption is big simultaneously, make and influenced its mass market process by the production cost height.
About synthesis of syndiotactic polymerizing styrene catalyzer, many with also having of non cyclopentadienyl catalyst class report, as the beta diketone titanium catalyzer respectively at 1996 at Chinese patent (application number: 96102496.8), 1999 at " polymer journal " (1999,671) and " applied chemistry " (2,001 20 (6):, 18 (2): 116) report oxine titanium catalyst " polymer journal " (1997,20 (6): report is arranged 746) in 1997.Its Primary Catalysts is non cyclopentadienyl catalyst.Normality is 90～98% between this two classes catalyzer institute synthetic syndiotactic polystyrene, fusing point is 263～273 ℃, cost is low though it has, long reaction time, reaction are controlled advantage easily, but because this two classes catalyzer is sterically hindered less relatively, catalytic activity is lower, and (catalytic activity is 1 * 10
4～0.5 * 10
6GPS/molTih), reduce and limited polymerization activity, make polymericular weight lower (molecular weight is about 100,000).This has just influenced the application performance of polymkeric substance, and is undesirable as the mechanical property of the engineering materials made with it.For this reason, the catalyzer of the syndiotactic polystyrene of the synthetic higher molecular weight of development is significant.2-hydroxyl benzophenone titanium class catalyzer has the characteristic of the syndiotactic polystyrene of synthetic higher molecular weight just.Up to now, still there is not the report that 2-hydroxybenzene ketone catalyzer is used for syndiotactic polymerization of phenylethylene.This work obtains state natural sciences fund, Tianjin natural science fund main project and Hebei province's natural science fund assistance respectively.
Summary of the invention
At the problems referred to above, the present invention has also overcome existing non cyclopentadienyl catalyst when overcoming metallocene catalyst class problem, when promptly the title complex of beta diketone titanium, oxine titanium carries out syndiotactic polymerization of phenylethylene, and the problem that polymericular weight is relatively low; A kind of catalyzer of 2-hydroxyl benzophenone titanium class is provided; Promptly utilize its distinctive ligand structure (electronic effect of part, bigger sterically hindered can the stabilizing active center), the polymericular weight that catalysis is obtained obviously improves; Thereby optimized the application performance of polymkeric substance.
Technical scheme of the present invention:
The 2-hydroxyl benzophenone titanium class catalyzer of synthesis of syndiotactic polystyrene is characterized in that it comprises following composition:
Primary Catalysts: 2-hydroxyl benzophenone titanium can be expressed as A
nTiL
4-n, n=1,2,3,4;
Wherein A is a part 2-hydroxyl benzophenone; L is auxiliary coordinating group;
The Primary Catalysts structural formula is as follows:
R, R ', R " be benzene ring substitution group group;
Promotor: alkylaluminoxane;
The mol ratio of promotor and Primary Catalysts (representing with Al/Ti) is 2000: 1～100: 1;
Promoter aluminium alkyl oxygen alkane can be methylaluminoxane (MAO); The mol ratio of promotor and Primary Catalysts (representing with Al/Ti) can be 1100: 1～200: 1.
Auxiliary coordination group L is a kind of in chlorine atom, alkoxyl group, phenoxy group or the substituent phenoxy in the above-mentioned Primary Catalysts 2-hydroxyl benzophenone titanium compound.Wherein alkoxyl group is a kind of in methoxyl group, oxyethyl group, propoxy-, isopropoxy, n-butoxy, isobutoxy or the tert.-butoxy; Substituent phenoxy is 2-methylphenoxy, 4-methylphenoxy, 6-methylphenoxy, 2,6-dimethyl phenoxy, 2-methoxyl group phenoxy group, 4-methoxyl group phenoxy group, 6-methoxyl group phenoxy group or 2, a kind of in the 6-dimethoxy phenoxy group.
The R of benzene ring substitution group on 2-hydroxyl benzophenone group be hydrogen atom, methyl, ethyl, propyl group, sec.-propyl,
A kind of in normal-butyl, isobutyl-, the tertiary butyl, methoxyl group, oxyethyl group, propoxy-, isopropoxy, n-butoxy, isobutoxy or the tert.-butoxy; R ', R " can be identical, can be different, be respectively a kind of in hydrogen atom, methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-or the tertiary butyl.
The 2-hydroxyl benzophenone titanium class Preparation of catalysts method of synthesis of syndiotactic polystyrene is: (wherein this compound is TiCl at room temperature the ether solution of part 2-hydroxyl benzophenone to be joined the compound of titanium and auxiliary coordination group L
4, alkyl titanate, metatitanic acid aryl ester) diethyl ether solution in carry out complex coordination, then rise to the solvent refluxing temperature, refluxed 6 hours, filter and washing precipitation, Primary Catalysts is made in vacuum-drying; Primary Catalysts mixes with promotor metering in molar ratio, forms 2-hydroxyl benzophenone titanium class catalyzer.
Catalyzer of the present invention, its purposes are that Primary Catalysts carries out syndiotactic polymerization of phenylethylene under the effect of promotor.Its Primary Catalysts concentration is 1 * 10
-5～1 * 10
-3Mol/L; Concentration range also can be 2 * 10
-4～1 * 10
-3Mol/L.This catalyst activity is 1 * 10
4～1 * 10
6GPS/molTih.Its polymerization temperature is 20～120 ℃, also can be 40～100 ℃.Polymerization time is 0.5～4h, also can be 1～3h; Acidifying ethanol termination reaction.The polymkeric substance that is settled out through washing and dry, can obtain syndiotactic polystyrene.Normality is 92～98% therebetween, and fusing point is 265～275 ℃, and molecular weight is 150,000～300,000.
Need to prove that catalyzer of the present invention also can be used for the syndiotactic polymerization of p-methylstyrene, cinnamic derivative.
Beneficial effect:
The invention provides a kind of 2-hydroxyl benzophenone titanium class catalyzer of synthesis of syndiotactic polystyrene.Its title complex with non cyclopentadienyl catalyst beta diketone titanium, 8 hydroxyquinoline titaniums different from the past.The peculiar structure of 2-hydroxyl benzophenone part, be that one of them Sauerstoffatom directly links to each other with phenyl ring, two phenyl ring are or not same plane, make the sterically hindered increasing of part, by the electronic effect of part, the bigger sterically hindered active centre of having stablized, elimination reaction is weakened, catalytic activity is improved, and polymericular weight obviously increases, and the syndiotactic polystyrene molecular weight is 150,000～300,000, compare with other non cyclopentadienyl catalyst, played the effect that improves polymericular weight.Thereby optimized the application performance of polymkeric substance, as improved the mechanical property of the engineering materials made from it.The raw material of synthetic this catalyzer is cheap, can react at normal temperature, is more suitable for industrialization.The present invention provides a kind of new catalyst for synthesis of syndiotactic polystyrene, and its catalytic activity is 1 * 10
4～1 * 10
6GPS/molTi.h.Other physicals such as degree of crystallinity, fusing points etc. of this product do not reduce, and catalyst activity voltinism longer duration can be kept and not reduce in two hours simultaneously, and its polymerization technique is easy, be easy to control, normality is 92～98% between the syndiotactic polystyrene that obtains, and fusing point is 265～275 ℃.Its production cost is lower than the external at present industrial cost with metallocene catalyst, thereby accelerates the commercialization of syndiotactic polystyrene scale operation.
Embodiment
Embodiment 1-10: structure, component and the relevant performance of synthetic catalyzer of the present invention, see table 1 for details.
Structure, component and the relevant performance table 1 of synthetic catalyzer of the present invention
Implement R R R Primary Catalysts Al/Ti T activity (* 10
5Normality T between gPS
mM
w(*
The example (℃)/molTih) % (℃) 10
4)
1 - CH
3 CH
3 A
2Ti(OPh)
2 1100 20 0.5 96 265 16
2 CH
3 C
2H
5 - ATiCl
3 500 80 8.3 93 270 23
3 C
3H
7 - CH
3 A
3TiCl 2000 80 0.9 94 275 18
4 CH
3 C
3H
7 C
2H
5 ATi(OPh)
3 700 40 7.1 98 269 17
5 CH
3O C
4H
9 C
3H
7 A
2TiCl
2 600 90 4.8 95 267 29
6 C
4H
9O CH
3 CH
3 ATi(OEt)
3 800 60 6.4 94 266 30
7 - C
2H
5 C
3H
7 ATi(OPhOMe)
3 400 80 3.2 96 270 24
8 CH
3 C
4H
9 CH
3 A
3TiCl 200 70 7.0 96 268 22
9 C
3H
5O - CH
3 A
2Ti(2，6-dmp)
2?500 20 10.2 97 266 20
10 CH
3O C
2H
5 - ATi(OEt)
3 600 120 7.4 98 265 25
Annotate: the A-part, the OEt-oxyethyl group, the OPh-phenoxy group, OPhOMe-methoxyl group phenoxy group, dmp-dimethyl phenoxy are executed example and are specified as follows:
Embodiment 1:
N at room temperature
2In be that 2-hydroxyl benzophenone 0.42g is dissolved in ether solution and joins and contains 1.5mlTi (OPh) with the part A of structure as shown in table 1
4Diethyl ether solution in carry out complex coordination, be warming up to the solvent refluxing temperature again, refluxed 6 hours, filter and washing precipitation, vacuum-drying obtains Primary Catalysts A
2Ti (OPh)
20.51g.Through nitrogen replacement and be equipped with in two mouthfuls of flasks of agitator, add the toluene that 15ml goes out through sodium Metal 99.5 reflux distillation at 100ml, stir and be warming up to 20 ℃, add Primary Catalysts A
2Ti (OPh)
2.0.47mg (concentration is 1.53 * 10
-5Mol/L), press the mol ratio of promotor and Primary Catalysts, promptly Al/Ti=1100 adds promotor triisobutyl alumina alkane 6.8ml, adds 20ml exsiccant vinylbenzene.Add 10% acidifying ethanolic soln behind the reaction 1h and cause reaction terminating.Reactant continues stirring 2h in excess ethyl alcohol, filter and alternately wash respectively three times with the second alcohol and water, and 70 ℃ of vacuum-drying 8h get polymkeric substance 0.41g.Normality is 96% therebetween, fusing point T
m(℃) be 265 ℃, molecular weight is 160,000, catalyst activity 0.5 * 10
5GPS/molTih.
Embodiment 2:
N at room temperature
2In be that 2-hydroxyl benzophenone 0.49g is dissolved in ether solution and joins and contains 1.7ml TiCl with the part A of structure as shown in table 1
4Ether solution in carry out complex coordination, be warming up to the solvent refluxing temperature again, refluxed filtration washing precipitation, vacuum-drying, the catalyst A TiCl of winner 6 hours
30.36g.Through nitrogen replacement and be equipped with in two mouthfuls of flasks of agitator, add the toluene that 15ml goes out through sodium Metal 99.5 reflux distillation at 100ml, stir down and be warming up to 80 ℃, adding Primary Catalysts ATiCl
320.6mg (concentration is 1 * 10
-3Mol/L), promotor is methylaluminoxane (MAO).Press the mol ratio of promotor and Primary Catalysts, promptly Al/Ti=500 adds promotor 3.7ml, adds 20ml exsiccant vinylbenzene.Add 10% acidifying ethanolic soln behind the reaction 1h and cause reaction terminating.Reactant continues stirring 2h in excess ethyl alcohol, filter and alternately wash respectively three times with the second alcohol and water, and 70 ℃ of vacuum-drying 8h get polymkeric substance 6.9g.Normality is 93% therebetween, and fusing point is 270 ℃, and molecular weight is 230,000, catalyst activity 8.3 * 10
5GPS/molTih.
Embodiment 3:
N at room temperature
2In be that 2-hydroxyl benzophenone 0.39g is dissolved in ether solution and joins and contains 1.5ml TiCl with the part A of structure as shown in table 1
3Diethyl ether solution in carry out complex coordination, be warming up to the solvent refluxing temperature again, refluxed 6 hours, filter and washing precipitation, vacuum-drying obtains Primary Catalysts A
3TiCl 0.27g.Through nitrogen replacement and be equipped with in two mouthfuls of flasks of agitator, add the toluene that 15ml goes out through sodium Metal 99.5 reflux distillation at 100ml, stir down and be warming up to 80 ℃, adding Primary Catalysts A
3(concentration is 1.7 * 10 to TiCl 3.02mg
-4Mol/L), press the mol ratio of promotor and Primary Catalysts, promptly Al/Ti=2000 adds promotor methylaluminoxane (MAO) 9.4ml, adds 20ml exsiccant vinylbenzene.Add 10% acidifying ethanolic soln behind the reaction 4h and cause reaction terminating.Reactant continues stirring 2h in excess ethyl alcohol, filter and alternately wash respectively three times with the second alcohol and water, and 70 ℃ of vacuum-drying 8h get polymkeric substance 1.12g.Normality is 94% therebetween, and fusing point is 275 ℃, and molecular weight is 180,000, catalyst activity 0.9 * 10
5GPS/molTih.
Embodiment 4:
N at room temperature
2In be that 2-hydroxyl benzophenone 0.51g is dissolved in ether solution and joins and contains 2.1mlTi (OPh) with the part A of structure as shown in table 1
4Diethyl ether solution in carry out complex coordination, be warming up to the solvent refluxing temperature again, refluxed 6 hours, filter and washing precipitation, vacuum-drying obtains Primary Catalysts ATi (OPh)
30.29g.Through nitrogen replacement and be equipped with in two mouthfuls of flasks of agitator, add the toluene that 15ml goes out through sodium Metal 99.5 reflux distillation at 100ml, stir down and be warming up to 40 ℃, adding Primary Catalysts ATi (OPh)
35.16mg (concentration is 1.606 * 10
-4Mol/L), press the mol ratio of promotor and Primary Catalysts, promptly Al/Ti=700 adds promotor triisobutyl alumina alkane (MAO) 4.1ml, adds 20ml exsiccant vinylbenzene.Add 10% acidifying ethanolic soln behind the reaction 1h and cause reaction terminating.Reactant continues to stir 2h in excess ethyl alcohol, filter and alternately respectively give a baby a bath on the third day after its birth inferiorly with the second alcohol and water, and 70 ℃ of vacuum-drying 8h must polymkeric substance 0.123g.Normality is 98% therebetween, and fusing point is 269 ℃, and molecular weight is 170,000, catalyst activity 7.1 * 10
5GPS/molTih.
Embodiment 5:
N at room temperature
2In be that 2-hydroxyl benzophenone 0.83g is dissolved in ether solution and joins and contains 1.6mlTiCl with the part A of structure as shown in table 1
4Diethyl ether solution in carry out complex coordination, be warming up to the solvent refluxing temperature again, refluxed 6 hours, filter and washing precipitation, vacuum-drying obtains Primary Catalysts A
2TiCl
20.56g.Through nitrogen replacement and be equipped with in two mouthfuls of flasks of agitator, add the toluene that 15ml goes out through sodium Metal 99.5 reflux distillation at 100ml, stir down and be warming up to 90 ℃, adding Primary Catalysts A
2TiCl
24.15mg (concentration is 1.16 * 10
-4Mol/L), press the mol ratio of promotor and Primary Catalysts, promptly Al/Ti=600 adds promotor methylaluminoxane (MAO) 5.5ml, adds 20ml exsiccant vinylbenzene.10% acidifying ethanolic soln causes reaction terminating behind the reaction 1h.Reactant continues stirring 2h in excess ethyl alcohol, filter and alternately wash respectively three times with the second alcohol and water, and 70 ℃ of vacuum-drying 8h get polymkeric substance 0.143g.Normality is 95% therebetween, and fusing point is 267 ℃, and molecular weight is 290,000, catalyst activity 4.8 * 10
5GPS/molTih.
Embodiment 6:
N at room temperature
2In be that 2-hydroxyl benzophenone 0.68g is dissolved in ether solution and joins and contains 1.8mlTi (OEt) with the part A of structure as shown in table 1
4Diethyl ether solution in carry out complex coordination, refluxed 6 hours, filter and washing precipitation, vacuum-drying obtains Primary Catalysts ATi (OEt)
30.45g.Through nitrogen replacement and be equipped with in two mouthfuls of flasks of agitator, add the toluene that 15ml goes out through sodium Metal 99.5 reflux distillation at 100ml, stir down and be warming up to 60 ℃, adding Primary Catalysts ATi (OEt)
38.65mg (concentration is 3.47 * 10
-4Mol/L), press the mol ratio of promotor and Primary Catalysts, promptly Al/Ti=800 adds promotor methylaluminoxane (MAO) 2.8ml, adds 20ml exsiccant vinylbenzene.Add 10% acidifying ethanolic soln behind the reaction 1h and cause reaction terminating.Reactant continues stirring 2h in excess ethyl alcohol, filter and alternately wash respectively three times with the second alcohol and water, and 70 ℃ of vacuum-drying 8h get polymkeric substance 0.205g.Normality is 94% therebetween, and fusing point is 266 ℃, and molecular weight is 300,000, catalyst activity 6.4 * 10
5GPS/molTih.
Embodiment 7:
N at room temperature
2In be that 2-hydroxyl benzophenone 0.39g is dissolved in ether solution and joins and contains 1.6mlTi (OPhOMe) with the part A of structure as shown in table 1
4Diethyl ether solution in carry out complex coordination, be warming up to the solvent refluxing temperature again, refluxed 6 hours, filter and washing precipitation, vacuum-drying obtains Primary Catalysts ATi (OPhOMe)
30.23g.Through nitrogen replacement and be equipped with in two mouthfuls of flasks of agitator, add the toluene that 15ml goes out through sodium Metal 99.5 reflux distillation at 100ml, stir down and be warming up to 80 ℃, adding Primary Catalysts ATi (OPhOMe)
310.282mg (concentration is 2.64 * 10
-4Mol/L), press the mol ratio of promotor and Primary Catalysts, promptly Al/Ti=400 adds promotor methylaluminoxane (MAO) 3.2ml, adds 20ml exsiccant vinylbenzene, adds 10% acidifying ethanolic soln behind the reaction 2h and causes reaction terminating.Reactant continues stirring 2h in excess ethyl alcohol, filter and alternately wash respectively three times with the second alcohol and water, and 70 ℃ of vacuum-drying 8h get polymkeric substance 0.325g.Normality is 96% therebetween, and fusing point is 270 ℃, and molecular weight is 240,000, catalyst activity 3.2 * 10
5GPS/molTih.
Embodiment 8:
N at room temperature
2In be that 2-hydroxyl benzophenone 0.64g is dissolved in ether solution and joins and contains 1.9mlTiCl with the part A of structure as shown in table 1
4Diethyl ether solution in carry out complex coordination, be warming up to the solvent refluxing temperature again, refluxed 6 hours, filter and washing precipitation, vacuum-drying obtains Primary Catalysts A
2TiCl
20.45g.Through nitrogen replacement and be equipped with in two mouthfuls of flasks of agitator, add the toluene that 15ml goes out through sodium Metal 99.5 reflux distillation at 100ml, stir down and be warming up to 70 ℃, adding Primary Catalysts A
2TiCl
217.3mg (concentration is 3.247 * 10
-4Mol/L), press the mol ratio of promotor and Primary Catalysts, promptly Al/Ti=200 adds promotor methylaluminoxane (MAO) 2.8ml, adds 20ml exsiccant vinylbenzene, adds 10% acidifying ethanolic soln behind the reaction 1h and causes reaction terminating.Reactant continues stirring 2h in excess ethyl alcohol, filter and alternately wash respectively three times with the second alcohol and water, and 70 ℃ of vacuum-drying 8h get polymkeric substance 0.1704g.Normality is 96% therebetween, and fusing point is 268 ℃, and molecular weight is 220,000, catalyst activity 7.0 * 10
5GPS/molTih.
Embodiment 9:
N at room temperature
2In with the part A of structure as shown in table 1 be 2-hydroxyl benzophenone 0.39g be dissolved in ether solution and join contain 1.7ml Ti (2,6-dmp)
4Diethyl ether solution in carry out complex coordination, be warming up to the solvent refluxing temperature again, refluxed 6 hours, filter and washing precipitation vacuum-drying, winner's catalyst A
2Ti (2,6-dmp)
20.25g.Through nitrogen replacement and be equipped with in two mouthfuls of flasks of agitator, add the toluene that 15ml goes out through sodium Metal 99.5 reflux distillation at 100ml, stir down and be warming up to 20 ℃, adding Primary Catalysts A
2Ti (2,6-dmp)
217.38mg concentration is 2.987 * 10
-4Mol/L), press the mol ratio of promotor and Primary Catalysts, promptly Al/Ti=500 adds promotor methylaluminoxane (MAO) 4.9ml, adds 20ml exsiccant vinylbenzene, adds 10% acidifying ethanolic soln behind the reaction 2h and causes reaction terminating.Reactant continues stirring 2h in excess ethyl alcohol, filter and alternately wash respectively three times with the second alcohol and water, and 70 ℃ of vacuum-drying 8h get polymkeric substance 0.1155g.Normality is 97% therebetween, and fusing point is 266 ℃, and molecular weight is 200,000, catalyst activity 10.2 * 10
5GPS/molTih.
Embodiment 10:
N at room temperature
2In be that 2-hydroxyl benzophenone 0.41g is dissolved in ether solution and joins and contains 1.8ml Ti (OEt) with the part A of structure as shown in table 1
4Diethyl ether solution in carry out complex coordination, be warming up to the solvent refluxing temperature again, refluxed 6 hours, filter and washing precipitation, vacuum-drying obtains Primary Catalysts ATi (OEt)
30.29g.Through nitrogen replacement and be equipped with in two mouthfuls of flasks of agitator, add the toluene that 15ml goes out through sodium Metal 99.5 reflux distillation at 100ml, be warming up to 120 ℃ under stirring, add Primary Catalysts ATi (OEt)
35.2mg (concentration is 2.03 * 10
-4Mol/L), press the mol ratio of promotor and Primary Catalysts, promptly Al/Ti=600 adds promotor methylaluminoxane (MAO) 5.3ml, adds 20ml exsiccant vinylbenzene, adds 10% acidifying ethanolic soln behind the reaction 0.5h and causes reaction terminating.Reactant continues to stir 2h in excess ethyl alcohol, filter and alternately respectively give a baby a bath on the third day after its birth inferiorly with the second alcohol and water, and 70 ℃ of vacuum-drying 8h must polymkeric substance 0.106g.Normality is 98% therebetween, and fusing point is 265 ℃, and molecular weight is 250,000, catalyst activity 7.4 * 10
5GPS/molTih.
Claims (7)
1, the 2-hydroxyl benzophenone titanium class catalyzer of synthesis of syndiotactic polystyrene is characterized in that it comprises following composition:
Primary Catalysts: 2-hydroxyl benzophenone titanium can be expressed as: A
nTiL
4-n, n=1,2,3,4;
Wherein A is a part 2-hydroxyl benzophenone; L is auxiliary coordinating group;
The Primary Catalysts structural formula is as follows:
R wherein, R ', R " be benzene ring substitution group group;
Auxiliary coordination group L is a kind of in chlorine atom, alkoxyl group, phenoxy group or the substituent phenoxy;
The R of benzene ring substitution group group is a kind of in hydrogen atom, methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, methoxyl group, oxyethyl group, propoxy-, isopropoxy, n-butoxy, isobutoxy or the tert.-butoxy; R ' of benzene ring substitution group group and R " can be identical, also can be different, be respectively a kind of in hydrogen atom, methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-or the tertiary butyl
Promotor: alkylaluminoxane;
The mol ratio of promotor and Primary Catalysts is that Al/Ti is 2000: 1～100: 1.
2, the 2-hydroxyl benzophenone titanium class catalyzer of synthesis of syndiotactic polystyrene according to claim 1 is characterized in that promoter aluminium alkyl oxygen alkane is methylaluminoxane (MAO); The molar ratio range of promotor and Primary Catalysts is that Al/Ti is 1100: 1～200: 1.
3, the 2-hydroxyl benzophenone titanium class catalyzer of synthesis of syndiotactic polystyrene according to claim 1 is characterized in that, described alkoxyl group is a kind of in methoxyl group, oxyethyl group, propoxy-, isopropoxy, n-butoxy, isobutoxy or the tert.-butoxy.
4, the 2-hydroxyl benzophenone titanium class catalyzer of synthesis of syndiotactic polystyrene according to claim 1, it is characterized in that, described substituent phenoxy is 2-methylphenoxy, 4-methylphenoxy, 6-methylphenoxy, 2, the 6-dimethyl phenoxy, 2-methoxyl group phenoxy group, 4-methoxyl group phenoxy group, 6-methoxyl group phenoxy group or 2, a kind of in the 6-dimethoxy phenoxy group.
5, the 2-hydroxyl benzophenone titanium class Preparation of catalysts method of the described synthesis of syndiotactic polystyrene of claim 1 is:
At room temperature the ether solution of part 2-hydroxyl benzophenone is joined the compound of titanium and auxiliary coordination group L, wherein this compound is TiCl
4, alkyl titanate, metatitanic acid aryl ester diethyl ether solution in carry out complex coordination, then rise to the solvent refluxing temperature, refluxed 6 hours, filter and washing precipitation, Primary Catalysts is made in vacuum-drying; Primary Catalysts mixes with promotor metering in molar ratio, forms 2-hydroxyl benzophenone titanium class catalyzer.
6, the purposes of the 2-hydroxyl benzophenone titanium class catalyzer of the described synthesis of syndiotactic polystyrene of claim 1 is that Primary Catalysts carries out syndiotactic polymerization of phenylethylene under the effect of promotor, and its Primary Catalysts concentration is 1 * 10
-5～1 * 10
-3Mol/L; This catalyst activity is 1 * 10
4～1 * 10
6GPS/molTih, its polymerization temperature are 20～120 ℃, and polymerization time is 0.5～4h, acidifying ethanol termination reaction, and the polymkeric substance that is settled out can obtain syndiotactic polystyrene through washing and dry; Normality is 92～98% therebetween, and fusing point is 265～275 ℃, and molecular weight is 150,000～300,000.
7, the purposes of the 2-hydroxyl benzophenone titanium class catalyzer of synthesis of syndiotactic polystyrene according to claim 6 is that Primary Catalysts carries out syndiotactic polymerization of phenylethylene under the effect of promotor, and its Primary Catalysts concentration is 2 * 10
-4～1 * 10
-3Mol/L; Polymerization temperature is 40～100 ℃; Polymerization time is 1～3h.
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