CN102746436A - Double peak and wide molecular weight distribution syndiotactic polystyrene polymer - Google Patents
Double peak and wide molecular weight distribution syndiotactic polystyrene polymer Download PDFInfo
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- CN102746436A CN102746436A CN2011100989759A CN201110098975A CN102746436A CN 102746436 A CN102746436 A CN 102746436A CN 2011100989759 A CN2011100989759 A CN 2011100989759A CN 201110098975 A CN201110098975 A CN 201110098975A CN 102746436 A CN102746436 A CN 102746436A
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Abstract
The invention relates to a wide molecular weight distribution syndiotactic polystyrene polymer to mainly solve a problem of bad processing property caused by the narrow molecular weight distribution of present syndiotactic polystyrene polymers. Syndiotactic polystyrene with the syndiotacticity being above 96%, the weight average molecular weight being 8*10<4>-70*10<4> and the molecular weight distribution being 15-100 is adopted in the invention, so the problem is well solved, and the polystyrene polymer in the invention can be widely applied to fields of hollow containers, tubes, engines and sheets.
Description
Technical field
The present invention relates to a kind of bimodal wide molecular weight distribution syndiotactic poly styrene polymer.
Background technology
The homogeneous catalysis system that cyclopentadiene titanium compound and promotor MAO (MAO) or boron fluorine cpd are formed is used for syndiotactic polymerization of phenylethylene and can obtains a normality at the syndiotactic polymer more than 96%.Melting point polymer is up to 270 ℃, and crystallization velocity is fast, chemically-resistant, and good heat resistance, narrow molecular weight distribution, dimensional stability is good, and has excellent electric performance, and its over-all properties can be compared with engineering plastics.The appearance of syndiotactic polystyrene (SPS) has caused people to its catalystsystem, particularly the research of Primary Catalysts metallocene compound.Document US 5252693 has reported that with EP210615 structure is CpTiCl
3And Cp*TiCl
3The catalystsystem of forming with promotor MAO is used for the situation of syndiotactic polymerization of phenylethylene, and wherein Cp is a cyclopentadienyl moiety, and Cp* is the pentamethyl-cyclopentadienyl moiety, but its catalytic activity and catalytic efficiency (are not high, poor stability, and industrial application value is little.Patent CN00119775.4, US5023222, US5045517 and US5196490 have reported the Cp*Ti (OR that present catalytic efficiency (is high
2OR
3)
3And Cp*Ti (OR)
3Type catalyzer (R is an alkyl or aryl), specific activity had significantly raising in the past, but the syndiotactic polystyrene MWD for preparing is narrower, between 1.5～2.5.This very poor than narrow molecular weight distributions syndiotactic polystyrene processing characteristics, restricted application in hollow container, film, tubing, cable, sheet material field.We gain enlightenment from the development of polyethylene product; Because the workability and the mechanical property of polyvinyl resin are conflicting; Improve molecular weight and can make product have better mechanical property, but resin becomes again and is difficult to processing simultaneously, and bimodal polyethylene can address this problem well.This product is made up of High molecular weight polyethylene and low molecular weight polyethylene two portions, and wherein High molecular weight polyethylene is in order to guarantee physical mechanics intensity, and low molecular weight polyethylene is in order to improve processing characteristics.The method of producing bimodal polyethylene mainly contains: 1. in same reactor drum, use 2 kinds of completely different and catalyzer independently, they respectively produce a kind of polyolefine with different molecular weight; 2. be employed in 2 and independently carry out sequential polymerisation reactions in the reactor drum; 3. the polymkeric substance that distributes different molecular weight mixes.But adopt the mode of multiple reactor sequential polymerization to invest greatly, and melt blended cost is high, and is difficult to mix.Therefore single reactor prepares the progress that the bimodal polyethylene technology is regarded as the property changed.
Summary of the invention
Technical problem to be solved by this invention is existing syndiotactic poly styrene polymer narrow molecular weight distribution; Thereby make the very poor defective of processing characteristics; A kind of bimodal wide molecular weight distribution syndiotactic poly styrene polymer is provided; It is wide that this syndiotactic poly styrene polymer has MWD, the characteristics of good processability.
In order to solve the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of bimodal wide molecular weight distribution syndiotactic poly styrene polymer, its link configuration unit have at least a among structural formula I, structural formula II or the structural formula II I:
N is the unitary number of iterations of link configuration in the formula;
Wherein the weight-average molecular weight of syndiotactic poly styrene polymer is greater than 8 * 10
4Extremely less than 70 * 10
4, MWD is 15～100.
Syndiotactic poly styrene polymer of the present invention uses one type of metallocene titanium compsn a), and its structure has following general formula:
Metallocene titanium compound A:CpTi (OR
1OR
2)
3With metallocene titanium compound B:Cp*Ti (OR
3OR
4)
3Mix forming compsn by a certain percentage, wherein Cp is a cyclopentadienyl moiety, and Cp* is the pentamethyl-cyclopentadienyl moiety, R
1, R
3For containing the alkyl of 2～6 carbon atoms, R
2, R
4For containing the alkyl of 1～4 carbon atom, Ti and R
2Between have Sauerstoffatom to link to each other, R
1With R
2, R
3With R
4Between all have Sauerstoffatom to link to each other.
The catalyzer initiation styrene polymerization of being made up of metallocene titanium compsn and alkylaluminoxane (or alkylaluminoxane and part triisobutyl aluminium substitution) makes.Measure polymkeric substance weight-average molecular weight and distribution (M with PL-GPC 220 then
w), measure polymkeric substance with Brucker AMX-400 nuclear magnetic resonance spectrometer
13Normality between C NMR.
Gather alkylaluminoxane and prepared by the aluminum alkyls control hydrolysis, hydrolytic reagent can be the water that contains in the inorganic salt of crystal water.The inorganic salt that contain crystal water can be CaCl
26H
2O, MgCl
26H
2O, CuSO
45H
2O, Al
2(SO
4)
318H
2O, CuSO
42H
2O, MgSO
47H
2O, FeSO
47H
2O, Ti (SO
4)
24H
2O, Ti
2(SO
4)
38H
2O or ZnSO
47H
2O etc.The mole ratio of aluminum alkyls and water is 1: 1～3.0, and temperature of reaction is-20～100 ℃, and the reaction times is 5～40 hours, and reaction solvent can be alkane and aromatic hydrocarbons.Aluminum alkyls commonly used has trimethylaluminium, triethyl aluminum, triisobutyl aluminium etc.Concrete steps are: aluminum alkyls is pressed Al/H
2The O mol ratio is 1: 1～2.5 under-20～0 ℃, slowly to be added dropwise to Al
2(SO
4)
318H
2In the toluene solution of O, the dropping time is 0.5～5 hour, after dropwising, makes temperature of reaction rise to 20～100 ℃, under this temperature, reacts 2～40 hours, and reaction with solid filtering, must contain the toluene solution that structure is the alkylaluminoxane of II after finishing.
In the there-necked flask of 100 milliliters of exsiccant, N
2Pump drainage 3 times, the CpTi (OCH of adding preset proportion
2CH
2OCH
3)
3And Cp*Ti (OCH
2CH
2OCH
3)
3, adding 50 milliliters of toluene, the normal temperature induction stirring makes compound dissolution, obtains double activity center's metallocene titanium compsn.
Polyreaction is preferably carried out between 50～90 ℃ at 30～130 ℃.In order to obtain the polymkeric substance of ideal performance, before reaction, earlier triisobutyl aluminium, alkylaluminoxane and cyclopentadiene titanium compound Cp*Ti (OC
6H
4OCH
3)
3Be placed in the toluene solution normal temperature ageing 10～30 minutes, and then carry out polymerization.Polymerization need be used the regular hour, and by several hours, preferably 1～10 hour, the ideal polymerization time depended on polymerization temperature and other polymerizing condition from several minutes.
Because traditional syndiotactic polystyrene is the metallocene-titanium catalyst that adopts single active center, causes the product molecular weight distribution that makes narrow; Owing to use double activity center's catalyzer, the product molecular weight distribution that makes is wide, improves processing characteristics greatly among the present invention.The MWD of tradition syndiotactic polystyrene is generally about 2, and the bimodal wide molecular weight distribution syndiotactic poly styrene polymer MWD among the present invention can be 15～100.Low 10 ℃ of the syndiotactic polystyrene of the comparable general narrow molecular weight distributions of polymer processing plasticization temperature has been obtained better technical effect.
Description of drawings
Fig. 1 is traditional syndiotactic polystyrene product G PC curve.
Fig. 2 adopts bimodal wide molecular weight distribution syndiotactic polystyrene product G PC curve among the present invention.
Fig. 1 obviously is a unimodal distribution, and MWD is very narrow, has only 1.9; Fig. 2 obviously is a bimodal distribution, and MWD is very wide, can reach 63.
Through embodiment the present invention is done further elaboration below.
Embodiment
[embodiment 1]
In the there-necked flask of 100 milliliters of exsiccant, N
2Pump drainage 3 times adds 0.1 mmole CpTi (OCH
2CH
2OCH
3)
3With 0.1 mmole Cp*Ti (OCH
2CH
2OCH
3)
3, mix mol ratio A: B=1: 1 adds 50 milliliters of toluene, and the normal temperature induction stirring makes compound dissolution, obtains double activity center's metallocene titanium compsn 1.
On 5 liters of mechanical stirring kettles, after 8 hours, lower the temperature N 90 ℃ of bakings earlier
2Pump drainage 3 times adds styrene monomer 1188 grams, and 35 ℃ of the interior temperature of system this moment contain 26.4 mmole triisobutyl aluminiums with the syringe injection; 52.8 mmole MAO adds the double activity center's metallocene titanium compsn 1 that contains preparation among the 0.107 mmole titanium embodiment 1, after catalyzer adds, and progressively chuck heating; About 40 minutes, make in the system 60 ℃ of temperature to polymerization temperatures, at 300 rev/mins of following stirring reactions after 4 hours, with ethanol-hydrochloric acid soln stopped reaction; Washing, dry that powder solid 766 restrains GPC curve such as Fig. 2 of this syndiotactic polystyrene product; Catalyst efficiency 120 kg of polymer/(gram titanium), a normality 97%, Mw=46 * 10
4, molecular weight distribution mw/mn=86.This formed product processing plasticizing temperature has only 262 ℃, low 12 ℃ of the syndiotactic polystyrene of comparable general narrow molecular weight distributions.
[embodiment 2]
In the there-necked flask of 100 milliliters of exsiccant, N
2Pump drainage 3 times adds 0.16 mmole CpTi (OCH
2CH
2OCH
3)
3With 0.04 mmole Cp*Ti (OCH
2CH
2O CH
2CH
3)
3, mix mol ratio A: B=4: 1 adds 50 ml n-hexanes, and the normal temperature induction stirring makes compound dissolution, obtains double activity center's metallocene titanium compsn 2.
On 5 liters of mechanical stirring kettles, after 8 hours, lower the temperature N 90 ℃ of bakings earlier
2Pump drainage 3 times adds styrene monomer 1188 grams, and 35 ℃ of the interior temperature of system this moment contain 26.4 mmole triisobutyl aluminiums with the syringe injection; 52.8 mmole MAO adds the double activity center's metallocene titanium compsn 2 that contains preparation among the 0.107 mmole titanium embodiment 2, after catalyzer adds, and progressively chuck heating; About 40 minutes, make in the system 60 ℃ of temperature to polymerization temperatures, at 300 rev/mins of following stirring reactions after 4 hours, with ethanol-hydrochloric acid soln stopped reaction; Washing, dry that powder solid 796 restrains GPC curve such as Fig. 2 of this syndiotactic polystyrene product; Catalyst efficiency 125 kg of polymer/(gram titanium), a normality 97%, Mw=46 * 10
4, molecular weight distribution mw/mn=58.This formed product processing plasticizing temperature has only 263 ℃, low 10 ℃ of the syndiotactic polystyrene of comparable general narrow molecular weight distributions.
[embodiment 3]
In the there-necked flask of 100 milliliters of exsiccant, N
2Pump drainage 3 times adds 0.15 mmole CpTi (OCH
2CH
2CH
2OCH
3)
3With 0.05 mmole Cp*Ti (OCH
2CH
2OCH
2CH
3)
3, mix mol ratio A: B=3: 1 adds 50 milliliters of hexanaphthenes, and the normal temperature induction stirring makes compound dissolution, obtains double activity center's metallocene titanium compsn 3.
On 5 liters of mechanical stirring kettles, after 8 hours, lower the temperature N 90 ℃ of bakings earlier
2Pump drainage 3 times adds styrene monomer 1188 grams, and 35 ℃ of the interior temperature of system this moment contain 26.4 mmole triisobutyl aluminiums with the syringe injection; 52.8 mmole MAO adds the double activity center's metallocene titanium compsn 3 that contains preparation among the 0.107 mmole titanium embodiment 3, after catalyzer adds, and progressively chuck heating; About 40 minutes, make in the system 60 ℃ of temperature to polymerization temperatures, at 300 rev/mins of following stirring reactions after 4 hours, with ethanol-hydrochloric acid soln stopped reaction; Washing, dry that powder solid 696 restrains GPC curve such as Fig. 2 of this syndiotactic polystyrene product; Catalyst efficiency 109 kg of polymer/(gram titanium), a normality 97%, Mw=12 * 10
4, molecular weight distribution mw/mn=68.This formed product processing plasticizing temperature has only 264 ℃, low 9 ℃ of the syndiotactic polystyrene of comparable general narrow molecular weight distributions.
[comparative example 1]
Except adding Cp*Ti (OCH
3)
3Single active center's metallocene titanium compound replaces double activity center's metallocene titanium compsn 1, and other condition is all identical with embodiment 1, and washing is dry that powder solid 720 restrains catalyst efficiency 112 kg of polymer/(gram titanium), a normality 97%, Mw=47 * 10
4, molecular weight distribution mw/mn=1.9.This formed product processing plasticizing temperature is up to 276 ℃, GPC curve such as Fig. 1 of this syndiotactic polystyrene product.
[comparative example 2]
Except adding Cp*Ti (OCH
2CH
2OCH
3)
3Single active center's metallocene titanium compound replaces double activity center's metallocene titanium compsn 2, and other condition is all identical with embodiment 2, and washing is dry that powder solid 716 restrains catalyst efficiency 111 kg of polymer/(gram titanium), a normality 97%, Mw=67 * 10
4, molecular weight distribution mw/mn=2.1.This formed product processing plasticizing temperature is up to 277 ℃, GPC curve such as Fig. 1 of this syndiotactic polystyrene product.
[comparative example 3]
Except adding Cp*Ti (OC
6H
5)
3Single active center's metallocene titanium compound replaces double activity center's metallocene titanium compsn 3, and other condition is all identical with embodiment 3, and washing is dry that powder solid 740 restrains catalyst efficiency 115 kg of polymer/(gram titanium), a normality 98%, Mw=70 * 10
4, molecular weight distribution mw/mn=1.8.This formed product processing plasticizing temperature is up to 279 ℃, GPC curve such as Fig. 1 of this syndiotactic polystyrene product.
Claims (1)
1. bimodal wide molecular weight distribution syndiotactic poly styrene polymer, its link configuration unit have at least a among structural formula I, structural formula II or the structural formula II I:
N is the unitary number of iterations of link configuration in the formula;
Wherein the weight-average molecular weight of syndiotactic poly styrene polymer is greater than 8 * 10
4Extremely less than 70 * 10
4, MWD is 15～100.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108456371A (en) * | 2018-02-07 | 2018-08-28 | 晖腾工业科技有限公司 | A kind of modified AS resin composite materials |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996020226A1 (en) * | 1994-12-23 | 1996-07-04 | WÜNSCH, Josef | Method of producing polymers of vinyl aromatic compounds using mixtures of metallocene catalyst systems |
| CN1285362A (en) * | 1999-08-19 | 2001-02-28 | 中国石油化工集团公司 | Catalyst for preparation of syndiotactic polystyrene |
-
2011
- 2011-04-20 CN CN2011100989759A patent/CN102746436A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996020226A1 (en) * | 1994-12-23 | 1996-07-04 | WÜNSCH, Josef | Method of producing polymers of vinyl aromatic compounds using mixtures of metallocene catalyst systems |
| CN1285362A (en) * | 1999-08-19 | 2001-02-28 | 中国石油化工集团公司 | Catalyst for preparation of syndiotactic polystyrene |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108456371A (en) * | 2018-02-07 | 2018-08-28 | 晖腾工业科技有限公司 | A kind of modified AS resin composite materials |
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Application publication date: 20121024 |