CN104262515B - A kind of granular random/stereoblock polystyrene preparation method - Google Patents
A kind of granular random/stereoblock polystyrene preparation method Download PDFInfo
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Abstract
A kind of granular random/stereoblock polystyrene preparation method, is related to a kind of preparation method of polymer.This method is polymerize using a kind of rare-earth catalysis system catalysis monomer styrene, a kind of granular random/stereoblock polystyrene of production.By controlling polymerization technology condition, regulation and control polymer molecular weight scope 1.6 × 104~1.0 × 106, melt 160 ~ 270 DEG C of scope of limit, stereoregularity polystyrene content 5 ~ 60%.With more preferable heat resistance, chemical proofing, dimensional stability and mechanical property；With stereoregularity polystyrene such as isotactic polystyrene（iPS）Or syndiotactic polystyrene（sPS）Compare, then significantly improve processing characteristics.Due to the special dissolubility of gained polystyrene and granular form, effectively avoid gluing the generation of kettle phenomenon present in body and suspension process.The polymerization system also contributes to the stability and monomer conversion of polymerization reaction system, simplifies polymerization technique and production equipment.
Description
Technical field
The present invention relates to a kind of method for producing polymer, more particularly to a kind of granular random/stereoblock polystyrene
Preparation method.
Background technology
Styrene monomer and its derivative can pass through radical polymerization, anionic polymerisation, cationic polymerization and polycomplexation
The different polymerizations such as close and realize polymerization, obtain it is random, complete with and with different stereoregularitys styrenic.It is many
The molecular structure of sample imparts the different performance range of polystyrene and different application fields.
Random polystyrene aPS possesses numerous performance advantages, such as water white transparency, and high-frequency dielectric and arc resistance are excellent,
Easy coloring, processability is excellent, but its random molecular chain structure causes its uncrystallizable, therefore aPS poor heat resistances, temperature in use
It is relatively low；Weather resisteant is poor, easy to change after by ultraviolet light；Chemical stability is poor.In addition, aPS is crisp, impact strength
It is low, easily there is stress cracking.IPS and sPS is regular due to strand, with highly crystalline, thus has than aPS higher resistance to
Hot, chemical proofing, dimensional stability and mechanical performance, but processing fluidity is poor, limits its extensive use.
Existing random polystyrene production technology mainly uses polymerisation in bulk, emulsion polymerization and suspension polymerisation.Body gathers
Technique is closed, the heat dissipation problem of system is generally solved using two sections of synthesis techniques, synthesis technique long flow path, equipment is complicated；Polymerization
Temperature is high（Generally at 80~110 DEG C）；Easily occurs glutinous kettle phenomenon in polymerization process, processing procedure is difficult, wastes time and energy.Suspend poly-
Close and emulsion polymerization technique is industrial conventional polystyrene synthesis technique at present, to avoid droplets from during the course of the reaction viscous
Knot is, it is necessary to add dispersant or emulsifying agent.But, the addition of dispersant or emulsifying agent causes in final polymerizate containing a small amount of
Dispersant or emulsifying agent residue, influence purity.The introducing of the impurity such as dispersant or emulsifying agent causes post-polymerization treatment technique
Complexity, loss of product is serious.The production method of complete same and syndiotactic polystyrene mainly has solwution method, slurry process and substance law.By
Easily crystallized in stereoregularity styrenic, thus solubility is very low in styrene monomer or other atent solvents.
Easily there is gel in the phase before polymerization, or even forms block.Thus need reaction unit that there is self-cleaning function and special stir
Mix device（CN 1683422A）.
Patent CN 102260362A are using Tetraheteropoly rare earth catalyst system and catalyzing neodymium naphthenate or carboxylic acid neodymium/alkyl aluminum/halogen-containing
Carboxylate/halogenated hydrocarbons is prepared for a kind of styrenic of random/many blocks of vertical structure.In order to regulate and control catalytic activity and vertical structure
The content of regularity polystyrene, has used two kinds of halogen sources.
The content of the invention
It is an object of the invention to provide the granular random/stereoblock polystyrene preparation method of one kind, this method is used
A kind of homogeneous ternary RE catalyst system and catalyzing carboxylic acid neodymium/alkyl aluminum/halogen-containing silane prepares granular random/stereoblock polyphenyl second
Alkene, halogen-containing silane is highly efficient as halogen source, therefore catalyst system and catalyzing has simpler chemical composition and synthesis technique.
The purpose of the present invention is achieved through the following technical solutions：
A kind of granular random/stereoblock polystyrene preparation method, methods described includes following preparation process：Using molten
Liquid or bulk technique, it is polymerizing styrene catalyzed using Ternary Homogeneous rare-earth catalysis system, under nitrogen protection to after baking
Injecting catalyst component A in ampoule bottle full of nitrogen, component B, component C and monomer, the ultrasonic aging 5 at -20~50 DEG C
~180min.Monomer styrene or derivatives thereof and solvent D are injected in polymerization bottle, the catalyst after ageing is transferred to polymerization
The h of polymerisation 0.5~48 is shaken in bottle at 20~70 DEG C；Added into polymerization system containing mass percentage concentration 5 ~ 10%
The ethanol solution of hydrochloric acid acidifying terminates polymerisation；Polymerizate is washed through ethanol precipitation, and 40 DEG C are dried under vacuum to constant weight, obtain
Partical E.
A kind of described granular random/stereoblock polystyrene preparation method, the product macromolecular chain is by random
Polystyrene block and complete same or syndiotactic polystyrene block are formed by connecting, and molecular weight of product scope 1.6 × 104~1.0 ×
106, stereoregularity polystyrene content 5 ~ 60% melts 160 ~ 270 DEG C of scope of limit.
A kind of described granular random/stereoblock polystyrene preparation method, the component A is major catalyst, is C6-
C10 carboxylic acid neodymium or neodymium naphthenate, such as neodymium octoate, or neodymium iso-octanate, n-nonanoic acid neodymium, capric acid neodymium, neodymium caprate, neodymium naphthenate, 2-
Thylhexoic acid neodymium, 3- thylhexoic acids neodymium, 2- ethyl enanthic acid neodymiums and 3- ethyl enanthic acid neodymiums.
Component B is co-catalyst, is alkyl aluminum class compound, is one or more of mixed in AlR3, AlHR2 and AlR2Cl
Compound, wherein AlR3 are such as trimethyl aluminium, or triethyl aluminum, tri-n-n-propyl aluminum, triisopropylaluminiuand, three n-butylaluminums, three isobutyls
Base aluminium, three amyl group aluminium, three hexyl aluminium, trioctylaluminum, ethyl di-p-tolyl aluminium；AlHR2 is such as dimethyl hydrogenated aluminium, or diethyl
Base aluminum hydride, diη-propyl aluminum hydride, di-n-butyl aluminum hydride, diisopropyl aluminum hydride, diisobutyl aluminium hydride, diamyl hydrogen
Change aluminium, dihexyl aluminum hydride, dioctyl aluminum hydride；AlR2Cl is such as dimethylaluminum chloride, or diethyl aluminum chloride, diη-propyl
Aluminium chloride, di-n-butyl aluminium chloride, diisopropyl aluminium chloride, diisobutyl aluminum chloride, diamyl aluminium chloride, dihexyl chlorination
Aluminium；
Component C is halogen source, is the one or more in halogen-containing organosilicon alkyl compound, and its molecular formula is SiR'
NX4-n, wherein R' are the one or more in H or C1 ~ C20 alkyl or its halides, and X is halogen, in being F, Cl, Br or I
One or more；Component C may be selected from：Silicon tetrachloride, trichlorosilane, methyl trichlorosilane, chloromethyl trichlorosilane, dichloro
Methyl trichlorosilane, ethyl trichlorosilane, propyltrichlorosilan, isopropyl base trichlorosilane, chloropropyl trichloro-silane, three chloropropyls
Trichlorosilane, normal-butyl trichlorosilane, isobutyl base trichlorosilane, amyl group trichlorosilane, cyclopenta trichlorosilane, n-hexyl trichlorine
Silane, n-heptyl trichlorosilane, 5- (bicycloheptyl) trichlorosilane, n-octyl trichlorosilane, iso-octyl trichlorosilane, n-nonyl
Trichlorosilane, positive decyl trichlorosilane, n-dodecane base trichlorosilane, n-tetradecane base trichlorosilane, n-hexadecyl trichlorine
Silane, n-octadecane base trichlorosilane, n-eicosane base trichlorosilane, phenyl trichlorosilane, chlorophenyl trichlorosilane, dichloro-benzenes
Base trichlorosilane, tetrachloro phenyl trichlorosilane, benzyl trichlorosilane, 4- chloromethylbenzenes base trichlorosilane, vinyl trichlorosilane,
Allyltrichlorosilane, cyclohexenyl group trichlorosilane, two rings（2,2,1）Hex- ethyl-trichlorosilane, 1,2- are double（Trichlorosilane）
Ethane, dimethyl dichlorosilane (DMCS),（Chloromethyl）Dimethyl dichlorosilane (DMCS), ethyl dichlorosilane, dimethyldichlorosilane, diethyl dichloro
Silane, Methylethyl dichlorosilane, diisopropyl dichlorosilane, isopropyl methyl dichlorosilane, 3- chloropropyl dichloro silicon
Alkane, di-t-butyl dichlorosilane, di-n-butyl dichlorosilane, methyl -3- chlorobutyls dichlorosilane, diamyl dichlorosilane, two
Hexyl dichlorosilane, hexyl methyl dichlorosilane, hept-ylmethyl dichlorosilane, dioctyl dichlorosilane, methyl dodecyl two
Chlorosilane, diphenyl dichlorosilane, diphenyl dichlorosilane, dichloromethyl phenylsilane, methylvinyldichlorosilane, pi-allyl
Dimethyl dichlorosilane (DMCS), 4- hexenyls dimethyl dichlorosilane (DMCS), 5- hexenyls dimethyl dichlorosilane (DMCS), 2-（4- cyclohexenyl groups）Ethyl-methyl
Dichlorosilane, trifluoropropylmethyldichlorosilane, perfluoro capryl dimethyl dichlorosilane (DMCS), perfluoro decyl dimethyl dichlorosilane (DMCS), diformazan
Base chlorosilane, diethyl chlorosilane, trim,ethylchlorosilane, CMDMCS chloromethyl dimethyl chlorosilane,（Dichloromethyl）Dimethylchlorosilane,
Chlorotriethyl silane, ethyl dimethylchlorosilane, propyl-dimethyl chlorosilane, isopropyl dimethylchlorosilane, positive definite base diformazan
Base chlorosilane, 7- octyldimethyl chlorosilanes, dimethyl octyl group chlorosilane, decyl dimethyl chlorosilane, dodecyl dimethyl
Chlorosilane, tri-phenyl chloride, methyldiphenyl base chlorosilane, tert-butyl diphenyl chlorosilane, 3- phenylpropyls dimethylchlorosilane,
To toluene dimethylchlorosilane, benzyl dimethyl chlorosilane, dichloromethyl vinyl chlorosilane, dimethylformamide dimethyl amino chlorine silicon
Alkane, methyclyloxypropyl dimethylchlorosilane,（3- cyanogen propyl group）Dimethylchlorosilane, tribromosilane, bromotrimethylsilane,
One or more of mixtures in triethyl group bromo-silicane.
Saturated alkane, cycloalkane, aromatic hydrocarbons and its alkyl-substituted isomers or above-mentioned solvent that solvent D is C5 ~ C12
Mixture is constituted；It is one or more of mixed in n-hexane, hexamethylene, normal heptane, normal octane, toluene, dimethylbenzene, ethylbenzene
Compound.
Mole of each component in a kind of described granular random/stereoblock polystyrene preparation method, the catalyst
Than for A：B：C=1：1~100：0.1~50.
A kind of described granular random/stereoblock polystyrene preparation method, the Aging Temperature that the system is used for-
20 ~ 50 DEG C, digestion time is 5 ~ 180min.
A kind of described granular random/stereoblock polystyrene preparation method, what the polymer was added when preparing urges
The mol ratio of agent and amount of monomer is A：Monomer=1：100~5000.
Solvent for use D is in a kind of described granular random/stereoblock polystyrene preparation method, the polymerization system
C5 ~ C12 saturated alkane, or the mixture of cycloalkane, aromatic hydrocarbons and its alkyl-substituted isomers or above-mentioned solvent are constituted；Choosing
From one or more of mixtures in n-hexane, hexamethylene, normal heptane, normal octane, toluene, dimethylbenzene, ethylbenzene.
A kind of described granular random/stereoblock polystyrene preparation method, the volume ratio of the monomer and solvent D is
Monomer：D=1：0~8.
A kind of described granular random/stereoblock polystyrene preparation method, the condition that the polymerisation is used for
Concussion reaction 0.5 ~ 48 hour under the conditions of 20 ~ 70 DEG C.
A kind of described granular random/stereoblock polystyrene preparation method, the pattern of the products therefrom E is particle
Shape.
Advantages of the present invention is with effect：
1. molecular weight of product scope of the present invention is 1.6 × 104~1.0 × 106, stereoregularity polystyrene content scope
5 ~ 60%, melt 160 ~ 270 DEG C of scope of limit.From material property, compared with random polystyrene, random/stereoblock polystyrene
With more preferable heat resistance, chemical proofing, dimensional stability and mechanical property；With stereoregularity polystyrene iPS
Or sPS is compared, then with the processing characteristics being obviously improved, and its black brittleness can be improved.From production technology, on the one hand, institute
Monomer can be dissolved in polymerization initial stage by obtaining randomly/stereoblock polystyrene, while crystalline stereoblock ensures poly- again
Close product to precipitate from solvent or monomer with the progress of polymerisation, form polymer beads.Therefore polymerization can be prevented
Thing reactor wall adhesion, caking, be prevented effectively from the generation of viscous kettle phenomenon.On the other hand, the stabilization of course of reaction is improved
Property, be conducive to improving monomer conversion.
2. the present invention uses solution or bulk technique, random/vertical structure is prepared using Ternary Homogeneous rare-earth catalysis system
The polystyrene of many blocks.Molecular weight of product scope 1.6 × 104~1.0 × 106, stereoregularity polystyrene content 5 ~
60%, limit scope is melted at 160 ~ 270 DEG C.From material property, compared with random polystyrene, random/stereoblock polystyrene
With more preferable heat resistance, chemical proofing, dimensional stability and mechanical property；Compared with stereoregularity polystyrene
Then there is more excellent processing characteristics, and can obviously improve its black brittleness.From production technology, resulting polymers are in polymerization initial stage
Monomer or solvent can be dissolved in, while crystalline stereoblock ensures polymerizate with the progress of polymerisation from solvent again
Or precipitated in monomer, form polymer beads.Therefore can prevent polymer reactor wall adhesion, caking, effectively
Avoid the generation of viscous kettle phenomenon.On the other hand, the stability of course of reaction is improved, is conducive to improving monomer conversion.
3. the polystyrene macromolecular chain of the invention is by random polystyrene block and a same or isotaxy polyphenyl second
Alkene block is formed by connecting.Wherein random polystyrene block makes the polystyrene have certain dissolving in monomer styrene
Property, and complete same or syndiotaxy regularity block then imparts the certain crystallizing power of the polystyrene.When the homogeneous rare earth of use
When catalyst system and catalyzing carries out solution or polymerisation in bulk, the polymer can be dissolved in monomer or solvent in polymerization initial stage, with polymerization
The increase of thing concentration, gradually is precipitated out to form polymer beads from monomer or solvent, therefore reduces polymer in reaction
The adhesion of wall, caking, it is therefore prevented that the generation of gel and block, effectively prevent the generation of viscous kettle phenomenon.From material
On energy, compared with random polystyrene aPS, such a random/stereoblock polystyrene has more preferable heat resistance, chemically-resistant medicine
Moral character, dimensional stability and mechanical property；With stereoregularity polystyrene such as isotactic polystyrene iPS or with vertical
Structure polystyrene sPS is compared, then with the processing characteristics being obviously improved.
Brief description of the drawings
The granule-morphology photo of random/stereoblock polystyrene of the gained of Fig. 1 embodiments 1；
The DSC curve of random/stereoblock polystyrene of the gained of Fig. 2 embodiments 5；
The petrographic microscope photo of random/stereoblock polystyrene of Fig. 3 embodiments 2 and the gained of embodiment 8；
The GPC spectrograms of Fig. 4 embodiments 1.
Embodiment
Illustrated embodiment below in conjunction with the accompanying drawings, the invention will be further described.
Embodiment 1
Under nitrogen protection the mmol of neodymium octoate 0.10, diethyl aluminum are injected into the ampoule bottle full of nitrogen after baking
2.00 mmol, the mmol of dichloro-diethyl silane 0.13 and 0.1 ml styrene, the ultrasonic aging 45min under the conditions of 20 DEG C.
The ml of styrene 11.4, the ml of n-hexane 10 are injected into polymerization bottle, the catalyst after ageing is transferred in polymerization bottle, at 50 DEG C
Concussion reaction 8h.The ethanol solution that the hydrochloric acid acidifying containing the % of mass percentage concentration 5~10 is added into polymerization bottle terminates polymerization
Reaction, reaction product is washed through ethanol precipitation, and 40 DEG C are dried under vacuum to constant weight, obtains granular random/stereoblock polystyrene
6.18 g, monomer conversion is 59.5 %, weight average molecular weight 4.61 × 105.
Embodiment 2
Under nitrogen protection the mmol of neodymium iso-octanate 0.14, triisobutyl are injected into the ampoule bottle full of nitrogen after baking
Aluminium 1.40 mmol, the mmol of dimethyl dichlorosilane (DMCS) 0.35 and 0.1 ml styrene, the min of ultrasonic aging 60 under the conditions of 35 DEG C.
The ml of styrene 12.8, the ml of toluene 15 are injected into polymerization bottle, the catalyst after ageing is transferred in polymerization bottle, is shaken at 40 DEG C
Swing 12 h of reaction.The ethanol solution that the hydrochloric acid acidifying containing the % of mass percentage concentration 5~10 is added into polymerization bottle terminates polymerization
Reaction, reaction product is washed through ethanol precipitation, and 40 DEG C are dried under vacuum to constant weight, obtains granular random/stereoblock polystyrene
8.89 g, monomer conversion is 76.2 %, weight average molecular weight 8.96 × 104.
Embodiment 3
The mmol of neodymium caprate 0.16, diisopropyl will be injected into the ampoule bottle full of nitrogen after baking under nitrogen protection
Base aluminium chloride 4.00 mmol, the mmol of propyltrichlorosilan 0.05 and 0.1 ml styrene, the ultrasonic aging 90 at 50 DEG C
min.The ml of styrene 7.32 is injected into polymerization bottle, the catalyst after ageing is transferred in polymerization bottle, concussion reaction at 55 DEG C
18 h.The ethanol solution that the hydrochloric acid acidifying containing the % of mass percentage concentration 5~10 is added into polymerization bottle terminates polymerisation, instead
Answer product to be washed through ethanol precipitation, 40 DEG C are dried under vacuum to constant weight, obtain the g of granular polystyrene 5.73, monomer conversion is
85.9 %, weight average molecular weight 7.62 × 104.
Embodiment 4
Under nitrogen protection the mmol of neodymium naphthenate 0.08, three normal-butyls are injected into the ampoule bottle full of nitrogen after baking
Aluminium 3.20 mmol, the mmol of chlorotriethyl silane 0.56 and 0.1 ml styrene, the min of ultrasonic aging 25 at 30 DEG C.To polymerization
The injection ml of styrene 18.3, toluene 10 ml, 40 DEG C of h of concussion reaction 10 in bottle.Added into polymerization bottle dense containing quality percentage
The ethanol solution for spending 5 ~ 10 % hydrochloric acid acidifying terminates polymerisation, and reaction product is washed through ethanol precipitation, 40 DEG C of vacuum drying
To constant weight, the g of granular polystyrene 9.95 is obtained, monomer conversion is 59.7 %, weight average molecular weight 5.72 × 105.
Embodiment 5
Under nitrogen protection the mmol of neodymium caprate 0.09, diethyl hydrogen are injected into the ampoule bottle full of nitrogen after baking
Change ultrasonic aging 30 at aluminium 2.70 mmol, the mmol of isopropyl methyl dichlorosilane 0.45 and 0.1 ml styrene, 10 DEG C
min.The ml of styrene 20.6, the ml of toluene 25, the h of concussion reaction 12 at 50 DEG C are injected into polymerization bottle.Added into polymerization bottle
The ethanol solution of hydrochloric acid acidifying containing the % of mass percentage concentration 5 ~ 10 terminates polymerisation, and reaction product is washed through ethanol precipitation
Wash, 40 DEG C are dried under vacuum to constant weight, obtain the g of granular polystyrene 16.83, monomer conversion is 89.5 %, weight average molecular weight
1.10×105。
Embodiment 6
Under nitrogen protection neodymium iso-octanate 0.11mmol, diisopropyl hydrogen are injected into the ampoule bottle full of nitrogen after baking
Change aluminium 0.55 mmol, the mmol of dimethyldichlorosilane 0.83 and 0.1 ml styrene, the ultrasonic aging 120 at 45 DEG C
min.The h of concussion reaction 5 at the ml of styrene 12.6, toluene 8 ml, 60 DEG C is injected into polymerization bottle, adds and contains into polymerization bottle
The ethanol solution of the % of mass percentage concentration 5 ~ 10 hydrochloric acid acidifying terminates polymerisation, and reaction product is washed through ethanol precipitation, and 40
DEG C constant weight is dried under vacuum to, obtains the g of granular polystyrene 5.18, monomer conversion is 45.1 %, weight average molecular weight 1.62 ×
104。
Embodiment 7
The mmol of neodymium caprate 0.16, diisopropyl will be injected into the ampoule bottle full of nitrogen after baking under nitrogen protection
Base aluminium chloride 8.00 mmol, the mmol of dimethyl dichlorosilane (DMCS) 0.16 and 0.1 ml styrene, the ultrasonic aging 180 at 50 DEG C
min.The ml of styrene 27.4, the ml of hexamethylene 11 are injected into polymerization bottle, the catalyst after ageing is transferred in polymerization bottle, 30
The h of concussion reaction 36 at DEG C.The ethanol solution termination that the hydrochloric acid acidifying containing the % of mass percentage concentration 5 is added into polymerization bottle is poly-
Reaction is closed, reaction product is washed through ethanol precipitation, and 40 DEG C are dried under vacuum to constant weight, obtain the g of granular polystyrene 13.08, it is single
Transformation rate is 52.3 %, weight average molecular weight 3.11 × 104.
Embodiment 8
The mmol of neodymium caprate 0.18, two positive fourths will be injected into the ampoule bottle full of nitrogen after baking under nitrogen protection
Base aluminium chloride 2.70 mmol, the mmol of isopropyl base trichlorosilane 0.18 and 0.1 ml styrene, the ultrasonic aging 5 at 40 DEG C
min.The ml of styrene 16.5 is injected into polymerization bottle, the catalyst after ageing is transferred in polymerization bottle, shakes anti-at 45 DEG C
Answer 12 h.The ethanol solution termination polymerisation that the hydrochloric acid containing the % of mass percentage concentration 5 ~ 10 is acidified is added into polymerization bottle,
Reaction product is washed through ethanol precipitation, and 40 DEG C are dried under vacuum to constant weight, obtains the g of granular polystyrene 13.83, monomer conversion
For 94.2 %, weight average molecular weight 2.84 × 105.
Embodiment 9
The mmol of capric acid neodymium 0.14, triisobutyl aluminium are injected into the ampoule bottle full of nitrogen after baking under nitrogen protection
14.00 mmol, the mmol of isopropyl methyl dichlorosilane 0.35 and 0.1 ml styrene, the ultrasonic aging 15 under the conditions of 0 DEG C
min.Styrene 48.01 ml, toluene 11ml are injected into polymerization bottle, the catalyst after ageing is transferred in polymerization bottle, 30
The h of concussion reaction 24 at DEG C.The ethanol solution that the hydrochloric acid acidifying containing the % of mass percentage concentration 5~10 is added into polymerization bottle is whole
Only polymerisation, reaction product is washed through ethanol precipitation, and 40 DEG C are dried under vacuum to constant weight, obtain granular polystyrene 20.03
G, monomer conversion is 45.8 %, weight average molecular weight 4.53 × 10.
Claims (1)
1. a kind of granular random/stereoblock polystyrene preparation method, it is characterised in that methods described includes following prepare and walked
Suddenly：It is polymerizing styrene catalyzed using Ternary Homogeneous rare-earth catalysis system using solution or bulk technique, under nitrogen protection
Injecting catalyst component A, component B, component C and monomer in the ampoule bottle of nitrogen are full of after to baking, is surpassed at -20~50 DEG C
Sound is aged 5~180min；Monomer styrene or derivatives thereof and solvent D are injected in polymerization bottle, the catalyst after ageing is turned
Move on to and shake the h of polymerisation 0.5~48 in polymerization bottle at 20~70 DEG C；Added into polymerization system dense containing quality percentage
The ethanol solution of the hydrochloric acid acidifying of degree 5 ~ 10% terminates polymerisation；Polymerizate is washed through ethanol precipitation, and 40 DEG C are dried under vacuum to
Constant weight, obtains partical E；
The product macromolecular chain is to be formed by connecting by random polystyrene block and complete same or syndiotactic polystyrene block, product
Molecular weight ranges 1.6 × 104~1.0 × 106, stereoregularity polystyrene content 5 ~ 60%, molten 160 ~ 270 DEG C of scope of limit；
The component A is major catalyst, is C6-C10Carboxylic acid neodymium, specially neodymium octoate, neodymium iso-octanate, n-nonanoic acid neodymium, capric acid neodymium,
Neodymium caprate, neodymium naphthenate, 2 ethyl hexanoic acid neodymium, 3- thylhexoic acids neodymium, 2- ethyl enanthic acid neodymiums and 3- ethyl enanthic acid neodymiums；
Component B is co-catalyst, is alkyl aluminum class compound, is AlR3、AlHR2And AlR2One or more of mixture in Cl,
Wherein AlR3It is trimethyl aluminium, or triethyl aluminum, tri-n-n-propyl aluminum, triisopropylaluminiuand, three n-butylaluminums, triisobutyl aluminium, three
Amyl group aluminium, three hexyl aluminium, trioctylaluminum, ethyl di-p-tolyl aluminium；AlHR2It is dimethyl hydrogenated aluminium, or diethylaluminum hydride,
Diη-propyl aluminum hydride, di-n-butyl aluminum hydride, diisopropyl aluminum hydride, diisobutyl aluminium hydride, diamyl aluminum hydride, two oneself
Base aluminum hydride, dioctyl aluminum hydride；AlR2Cl is dimethylaluminum chloride, or diethyl aluminum chloride, diη-propyl aluminium chloride, two are just
Butyl aluminium chloride, diisopropyl aluminium chloride, diisobutyl aluminum chloride, diamyl aluminium chloride, dihexylaluminum chloride；
Component C is halogen source, is the one or more in halogen-containing organosilicon alkyl compound, and its molecular formula is SiR'nX4-n, its
Middle R' is H or C1~C20Alkyl or its halides in one or more, X is halogen, is one kind or several in F, Cl, Br or I
Kind；Component C may be selected from：Trichlorosilane, methyl trichlorosilane, chloromethyl trichlorosilane, dichloromethyl trichlorosilane, ethyl three
Chlorosilane, propyltrichlorosilan, isopropyl base trichlorosilane, chloropropyl trichloro-silane, three chloropropyl trichloro-silanes, normal-butyl trichlorine
Silane, isobutyl base trichlorosilane, amyl group trichlorosilane, cyclopenta trichlorosilane, n-hexyl trichlorosilane, n-heptyl trichlorine silicon
Alkane, 5- (bicycloheptyl) trichlorosilane, n-octyl trichlorosilane, iso-octyl trichlorosilane, n-nonyl trichlorosilane, positive decyl three
Chlorosilane, n-dodecane base trichlorosilane, n-tetradecane base trichlorosilane, hexadecane base trichlorosilane, n-octadecane base three
Chlorosilane, n-eicosane base trichlorosilane, phenyl trichlorosilane, chlorophenyl trichlorosilane, dichlorophenyl trichlorosilane, tetrachlorobenzene
Base trichlorosilane, benzyl trichlorosilane, 4- chloromethylbenzenes base trichlorosilane, vinyl trichlorosilane, allyltrichlorosilane, ring
Hexenyltrichlorosilane, two rings（2,2,1）Hex- ethyl-trichlorosilane, 1,2- are double（Trichlorosilane）Ethane, dimethyl dichlorosilane (DMCS),
（Chloromethyl）Dimethyl dichlorosilane (DMCS), ethyl dichlorosilane, dimethyldichlorosilane, diethyl dichlorosilane, Methylethyl dichloro
Silane, diisopropyl dichlorosilane, isopropyl methyl dichlorosilane, 3- chloropropyls dichlorosilane, di-t-butyl dichloro silicon
Alkane, di-n-butyl dichlorosilane, methyl -3- chlorobutyls dichlorosilane, diamyl dichlorosilane, dihexyl dichlorosilane, hexyl
Dimethyl dichlorosilane (DMCS), hept-ylmethyl dichlorosilane, dioctyl dichlorosilane, methyl dodecyl dichlorosilane, phenyl dichloro silicon
Alkane, diphenyl dichlorosilane, dichloromethyl phenylsilane, methylvinyldichlorosilane, allyl methyl dichlorosilane, 4- oneself
Enylmethyl dichlorosilane, 5- hexenyls dimethyl dichlorosilane (DMCS), 2-（4- cyclohexenyl groups）Ethyl-methyl dichlorosilane, trifluoro propyl
Dimethyl dichlorosilane (DMCS), perfluoro capryl dimethyl dichlorosilane (DMCS), perfluoro decyl dimethyl dichlorosilane (DMCS), dimethylchlorosilane, diethyl chlorine
Silane, trim,ethylchlorosilane, CMDMCS chloromethyl dimethyl chlorosilane,（Dichloromethyl）Dimethylchlorosilane, chlorotriethyl silane, ethyl
Dimethylchlorosilane, propyl-dimethyl chlorosilane, isopropyl dimethylchlorosilane, positive definite base dimethylchlorosilane, 7- octyl groups two
Methylchlorosilane, dimethyl octyl group chlorosilane, decyl dimethyl chlorosilane, dodecyl dimethyl chlorosilane, triphenyl chlorine silicon
Alkane, methyldiphenyl base chlorosilane, tert-butyl diphenyl chlorosilane, 3- phenylpropyls dimethylchlorosilane, to toluene dimethyl chloride silicon
Alkane, benzyl dimethyl chlorosilane, dichloromethyl vinyl chlorosilane, dimethylformamide dimethyl amino chlorosilane, methylacryloyl third
Base dimethylchlorosilane,（3- cyanogen propyl group）In dimethylchlorosilane, tribromosilane, bromotrimethylsilane, triethyl group bromo-silicane
One or more of mixtures；
Solvent D is C5~C12Saturated alkane, cycloalkane, the mixing of aromatic hydrocarbons and its alkyl-substituted isomers or above-mentioned solvent
Thing is constituted；One or more of mixing in n-hexane, hexamethylene, normal heptane, normal octane, toluene, dimethylbenzene, ethylbenzene
Thing；
The mol ratio of each component is A in the catalyst：B：C=1：1~100：0.1~50；
The Aging Temperature that the system is used is -20 ~ 50 DEG C, and digestion time is 5 ~ 180min；
The catalyst and the mol ratio of amount of monomer that the polymer is added when preparing are A：Monomer=1：100~5000；
The monomer and solvent D volume ratio are monomer：D=1：0~8；
The condition that the polymerisation is used for 20 ~ 70 DEG C under the conditions of concussion reaction 0.5 ~ 48 hour；
The pattern of the products therefrom E is graininess.
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