CN101747461B - Polymer containing hydroxystyrene on side group, preparation method and application thereof - Google Patents
Polymer containing hydroxystyrene on side group, preparation method and application thereof Download PDFInfo
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- CN101747461B CN101747461B CN 200810239501 CN200810239501A CN101747461B CN 101747461 B CN101747461 B CN 101747461B CN 200810239501 CN200810239501 CN 200810239501 CN 200810239501 A CN200810239501 A CN 200810239501A CN 101747461 B CN101747461 B CN 101747461B
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Abstract
The invention relates to polymer containing hydroxystyrene on a side group, preparation method and application thereof. The preparation method comprises the following steps of: firstly, preparing a type of styrene derivative monomers capable of positive (negative) ion polymerization through a Grignard reaction and a hydroxystyrene protection reaction, i.e. tert-butyl dimethyl silica ethyl styrene and tert-butyl dimethyl silica propyl styrene; then preparing a homopolymer and a segmented copolymer of the tert-butyl dimethyl silica ethyl styrene or the tert-butyl dimethyl silica propyl styrene through a positive (negative) ion polymerization method; and finally, preparing the polymers into a polymer containing hydroxystyrene on a side group through a hydrolysis reaction. The invention has the advantage that the side group of the polymer finally prepared by hydrolysis contains a hydrophilic group, and the polymer has excellent blood compatibility. The polymer containing hydroxystyrene on the side group can be applied to biomedical materials comprising bracket materials, cartilage materials, drug slow release materials and vessel materials.
Description
Technical field
The present invention relates to polymer polymerizing, preparation method and its usage, more particularly, the present invention relates to polymkeric substance, preparation method and its usage that side group contains hydroxy styrenes, by positively charged ion or anionic polymerisation process, the preparation side group contains homopolymer and the segmented copolymer of hydroxy styrenes.
Background technology
The performance that many uniquenesses are arranged based on the thermoplastic elastomer of polyisobutene, as good mechanical property, toughness, chemical stability, barrier property and good processing characteristics and returnability, and in the main chain of polymkeric substance, tertiary carbon atom and secondary carbon(atom) alternative arrangement, this makes the thermoplastic elastomer based on iso-butylene that good biologically stable and biocompatibility be arranged, a kind of good biologically inert medical material.At U.S.Patent5,741,331, U.S.Patent 6,102,939 and U.S.Patent 6,197,240 reported the research of polyisobutene-b-polystyrene as biomaterial, but this class material hydrophilicity is poor.Many polar monomers can not be participated in cationoid polymerisation directly.The method that combines with other polymerizations (as anionoid polymerization, radical polymerization, ring-opening polymerization) by cationoid polymerisation improve polymer hydrophilicity can difficulty very large, and a lot of mechanism it be unclear that.the people such as Faust have reported the monomer of the cationically polymerizable that contains blocking group, as tertiary butyl dimethyl Si base vinylbenzene (Biomacromolecules, 2005, 6, 2570-2582), to uncle's oxygen base vinylbenzene (J.Macromol.Sci., Pure Appl.Chem., 2007, A44, 359-366), (Macromolecules 2005 to tert-Butyl vinyl ether, 38, 8183-8191), the polymkeric substance that contains blocking group by the synthetic side group of controlled/living cationic polymerization, polymkeric substance further hydrolysis obtains the polymkeric substance that side group contains hydroxyl, improved well the hydrophilicity of polymkeric substance.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art part, and a kind of performance is provided good side group contains polymkeric substance, the preparation method and its usage of hydroxy styrenes.
The object of the invention can be achieved by the following measures:
Side group contains the polymkeric substance of hydroxy styrenes: in sun/anionoid polymerization, prepare side group and contain the segmented copolymer that hydroxy styrenes homopolymer, side group contain hydroxy styrenes; Wherein:
Side group contains the homopolymer of hydroxy styrenes: each structural unit of polymkeric substance contains hydroxyl, and the number-average molecular weight scope is 2000～200000g/mol, and molecular weight distribution is between 1.1～5.0;
Side group contains the segmented copolymer of hydroxy styrenes: contain the hydroxyl polystyrene and partly account for whole molecular chain 10～40% mass percents, segmented copolymer number-average molecular weight scope is 20000～500000g/mol, and molecular weight distribution is between 1.1～5.0.
Described hydroxy styrenes segmented copolymer monomer refers to: iso-butylene, diolefine; Diolefine comprises isoprene, divinyl;
The preparation method that side group contains hydroxy polymer was divided into for three steps:
(1) styrene derivatives is synthetic: comprise the synthetic of tert-butyl dimethyl silica ethyl vinylbenzene and tertiary butyl dimethyl Si propylstyrene:
Take the 4-bromstyrol as raw material, temperature of reaction is the 0-70 degree, generates 4-(2-hydroxyethyl) vinylbenzene by Grignard reagent and reacting ethylene oxide; Due in the anion/cation polymerization process, hydroxyl can participate in chain termination reaction, therefore, hydroxyl protection must be got up before polymerization.By TERT-BUTYL DIMETHYL CHLORO SILANE, hydroxyl is protected, imidazoles is catalyzer, prepare tert-butyl dimethyl silica ethyl vinylbenzene after reaction, wherein the molar ratio between magnesium, 4-bromstyrol and oxyethane is 1: 0.8～1.2: 1.0～4.0; Molar ratio 1: 1.0～2.0: 1.0～2.0 between 4-(2-hydroxyethyl) vinylbenzene, TERT-BUTYL DIMETHYL CHLORO SILANE and imidazoles;
Tert-butyl dimethyl silica ethyl vinylbenzene: the pungency colourless oil liquid, boiling point: 98 ℃, 1～2mb, density is: 1.205g/cm
3
Take the 4-bromstyrol as raw material; temperature of reaction is the 0-70 degree; generate 4-(3-hydroxypropyl) vinylbenzene by Grignard reagent and propylene oxide reaction; then by TERT-BUTYL DIMETHYL CHLORO SILANE, hydroxyl is protected; imidazoles is catalyzer, prepares the tertiary butyl dimethyl Si propylstyrene after reaction.Wherein the molar ratio between magnesium, 4-bromstyrol and propylene oxide is 1: 0.8～1.2: 1.0～4.0; Molar ratio 1: 1.0～2.0: 1.0～2.0 between 4-(2-hydroxypropyl) vinylbenzene, TERT-BUTYL DIMETHYL CHLORO SILANE and imidazoles;
The tertiary butyl dimethyl Si propylstyrene: the pungency colourless oil liquid, boiling point: 105 ℃, 1～2mb, density is: 1.255g/cm
3
(2) homopolymer of styrene derivatives and segmented copolymer is synthetic:
In cationoid polymerisation, under cold condition, 0～-100 ℃, with methyl chloride or methyl chloride and mixed alkane solvent, methyl chloride and alkane volume ratio are 1.0: 0.1～5.0, then add initiator, the 3rd component and coinitiator respectively in mixed solvent, and initiator concentration is: 1mol/L～10
-5Mol/L, coinitiator concentration is 10mol/L～10
-4Mol/L, the 3rd concentration of component is: 0.1mol/L～10
-6Mol/L, initiator, the 3rd component and coinitiator molar ratio are 1.0: 0.1～10: 1.0～60, add subsequently above-mentioned monomer tert-butyl dimethyl silica ethyl vinylbenzene or tertiary butyl dimethyl Si propylstyrene to prepare homopolymer, or prepare iso-butylene and tert-butyl dimethyl silica ethyl styrene block copolymer or iso-butylene and tertiary butyl dimethyl Si propylstyrene segmented copolymer by the mode that order adds pan feeding.Polymerization time is 30 minutes～24 hours; Monomer concentration 0.5mol/L～20mol/L wherein, iso-butylene and tert-butyl dimethyl silica ethyl vinylbenzene or with the mass ratio of tertiary butyl dimethyl Si propylstyrene charging capacity be 0.5～50: 0.5; Polymkeric substance is at last by methanol extraction, washing, drying;
The styrene derivatives homopolymer: the number-average molecular weight scope is 2000～200000g/mol, and molecular weight distribution is between 1.1～5.0;
The styrene derivatives segmented copolymer: polystyrene derivative partly accounts for whole molecular chain 10～40% mass percents, and segmented copolymer number-average molecular weight scope is 20000～500000g/mol, and molecular weight distribution is between 1.1～5.0;
In anionoid polymerization, take alkane as solvent, butyllithium is initiator, and initiator concentration is 1mol/L～10
-5Mol/L, above-mentioned monomer tert-butyl dimethyl silica ethyl vinylbenzene or tertiary butyl dimethyl Si propylstyrene prepare homopolymer; Or add mode preparation tert-butyl dimethyl silica ethyl vinylbenzene and the segmented copolymer of diolefine (as isoprene, divinyl) and the segmented copolymer of tertiary butyl dimethyl Si propylstyrene and diolefine (as isoprene, divinyl) of pan feeding, polymerization time 1～20 hour by order; Diolefine and tert-butyl dimethyl silica ethyl vinylbenzene or with the mass ratio of tertiary butyl dimethyl Si propylstyrene charging capacity be 0.5～50: 0.5, homopolymer or multipolymer are by methanol extraction, washing, final drying.
(3) side group contains the hydrolysis preparation of the polymkeric substance of hydroxy styrenes: the homopolymer of styrene derivatives and segmented copolymer are hydrolyzed at tetrahydrofuran (THF) and N; in the mixed solvent of dinethylformamide; wherein tetrahydrofuran (THF) and N; the dinethylformamide volume ratio is 1: 0.1～10; under the effect of n-butyl ammonium fluoride; deviate from blocking group, generating side group is polystyrene homopolymer or the segmented copolymer of hydroxyethyl and hydroxypropyl, and n-butyl ammonium fluoride concentration is 0.02～2mol/L.
Described styrene derivatives homopolymer refers to poly-tert-butyl dimethyl silica ethyl vinylbenzene, poly-tertiary butyl dimethyl Si propylstyrene.
In cationoid polymerisation:
Described initiator is 2-chloro-2,4, a kind of in 4-trimethylpentane TMPCl or water; Described the 3rd component is a kind of in hexahydropyridine or 2,6-di-tert-butyl pyridine; Described coinitiator is a kind of in titanium tetrachloride, aluminum chloride, a chloroethyl aluminium and ethyl aluminum dichloride.
The segmented copolymer of described iso-butylene and styrene derivatives prepares by cationoid polymerisation; The segmented copolymer of described diolefine and styrene derivatives prepares by anionoid polymerization.
The segmented copolymer that described side group contains hydroxyl comprises: polyhutadiene-b-poly-hydroxyethyl vinylbenzene, the poly-hydroxypropyl vinylbenzene of polyhutadiene-b-, polyisoprene-b-poly-hydroxyethyl vinylbenzene, the poly-hydroxypropyl vinylbenzene of polyisoprene-b-, the poly-hydroxypropyl vinylbenzene of polyisobutene-b-and polyisobutene-b-poly-hydroxyethyl vinylbenzene.Segmented copolymer and the segmented copolymer hydrolysis of tertiary butyl dimethyl Si propylstyrene and diolefine (as isoprene, divinyl) of these polymkeric substance by iso-butylene and tert-butyl dimethyl silica ethyl styrene block copolymer, iso-butylene and tertiary butyl dimethyl Si propylstyrene segmented copolymer, tert-butyl dimethyl silica ethyl vinylbenzene and diolefine (as isoprene, divinyl) obtains.
Side group contains the purposes of the polymkeric substance of hydroxy styrenes, is used for bio-medical material, comprises timbering material, cartilage material, Thermosensitive Material Used for Controlled Releasing of Medicine and vascular grafts.
Tert-butyl dimethyl silica ethyl vinylbenzene, tertiary butyl dimethyl Si propylstyrene are namely the monomers of cationoid polymerisation, are also the monomers of anionoid polymerization.
Side group contains the polymkeric substance of hydroxy styrenes, comprising: the polystyrene homopolymer of hydroxyethyl and hydroxypropyl.It obtains by tert-butyl dimethyl silica ethyl styrene homopolymers, the hydrolysis of tertiary butyl dimethyl Si propylstyrene homopolymer.
The method that the present invention also provides blocking group to remove.N-butyl ammonium fluoride is a kind of potent agent that removes the silicane blocking group, due to very strong avidity (142kcal/mol), F being arranged between F and Si atom
-Can make Si-O key (112kcal/mol) fracture, thereby well remove the silicane blocking group.And remove reaction process and avoided use strong acid, highly basic and strong oxidizer, fully guarantee the backbone structure integrity.
The homopolymer and the segmented copolymer that prepare by cationic polymerization process comprise: poly-tert-butyl dimethyl silica ethyl vinylbenzene, poly-tertiary butyl dimethyl Si propylstyrene, the poly-tert-butyl dimethyl silica ethyl styrene block copolymer of polyisobutene-b-, the poly-tertiary butyl dimethyl Si propylstyrene segmented copolymer of polyisobutene-b-.
The homopolymer and the segmented copolymer that prepare by anionic polymerisation process comprise: poly-tert-butyl dimethyl silica ethyl vinylbenzene, the segmented copolymer of poly-tertiary butyl dimethyl Si propylstyrene, tert-butyl dimethyl silica ethyl vinylbenzene and diolefine (as isoprene, divinyl) and the segmented copolymer of tertiary butyl dimethyl Si propylstyrene and diolefine (as isoprene, divinyl).
The present invention compared with prior art has following advantage: compare with polystyrene, poly-(iso-butylene-b-vinylbenzene) section multipolymer, poly-(isoprene-b-vinylbenzene) section multipolymer and poly-(divinyl-b-vinylbenzene) segmented copolymer, polymkeric substance in the present invention contains hydroxyl, have hydrophilicity preferably, improve the hydrophilicity of material and improve printing and dyeing performance, adhesiveproperties.
Description of drawings
Fig. 1 is tert-butyl dimethyl silica ethyl vinylbenzene synthetic route chart of the present invention
Fig. 2 is the synthetic route chart of tertiary butyl dimethyl Si propylstyrene of the present invention
Fig. 3 is the cationoid polymerisation route map of the poly-tertiary butyl dimethyl Si propylstyrene of the present invention
Fig. 4 is the cationoid polymerisation route map of the poly-tertiary butyl dimethyl Si propylstyrene segmented copolymer of polyisobutene-b-of the present invention
Fig. 5 is the anionoid polymerization route map of the poly-tertiary butyl dimethyl Si propylstyrene of the present invention
Fig. 6 is tert-butyl dimethyl silica ethyl vinylbenzene 1H-NMR spectrogram of the present invention
Fig. 7 is the poly-cinnamic 1H-NMR spectrograms of tert-butyl dimethyl silica ethyl of three the present invention
Fig. 8 is the cinnamic 1H-NMR spectrogram of poly-hydroxyethyl of the present invention
Embodiment
The below enumerates 3 embodiment, and by reference to the accompanying drawings, the present invention is further illustrated, but the present invention is not only limited to these embodiment.
(1), the cinnamic preparation of tert-butyl dimethyl silica ethyl
In the 500mL there-necked flask of magnetic agitation, constant pressure funnel, reflux condensing tube is housed, keeping adding 1.488g (0.062mol) through the magnesium chips of polished finish under the anaerobic anhydrous condition, the 40mL anhydrous tetrahydro furan is as solvent, pass into N2, dropping is dissolved in 11.33g (0.062mol) the 4-bromstyrol solution in the 70mL tetrahydrofuran (THF), and temperature is controlled at below 40 ℃.After dropwising, continuing reaction, until reactive magnesium is complete.Sherwood oil with precooling cools to mixture-15 ℃, adds rapidly the mixing solutions of oxyethane (3.83g, 0.087mol) and 80mL anhydrous tetrahydro furan, after adding, at room temperature continues reaction 3h.Molar ratio between magnesium, 4-bromstyrol, oxyethane is 1: 1: 1.4.Under 0 ℃, after adding ether 100mL, slowly drip 100mL saturated ammonium chloride solution hydrolysis, then with anhydrous diethyl ether extraction 3 times, oil reservoir with a large amount of deionized water rinsings until solution is neutrality.The oil reservoir of gained is with more than anhydrous sodium sulfate drying 24h, and underpressure distillation is collected 81 ℃, and 1mb left and right cut obtains 4-(2-hydroxyethyl) vinylbenzene 6.5g (productive rate: 70%) pungency colourless oil liquid.
In the 500mL there-necked flask of magnetic agitation, constant pressure funnel, reflux condensing tube is housed, keeping under the anaerobic anhydrous condition, add 4-(2-hydroxyethyl) vinylbenzene (14.8g, 0.10mol), imidazoles (7.49g, 0.11mol), 100mL DMF solvent, under 0 ℃, progressively drip the DMF solution of 100mL TERT-BUTYL DIMETHYL CHLORO SILANE (16.58g, 0.11mol).Molar ratio between 4-(2-hydroxyethyl) vinylbenzene, TERT-BUTYL DIMETHYL CHLORO SILANE and imidazoles is 1: 1.1: 1.1.After dropwising, at room temperature react 24h.Reaction mixture is poured into 200mL CH
2Cl
2In, then rinse with 200mL 5%KOH solution, oil reservoir with a large amount of deionized water rinsings until solution is neutrality.The oil reservoir of gained is with more than anhydrous sodium sulfate drying 24h, and underpressure distillation is collected 98 ℃, and 1mb left and right cut obtains tert-butyl dimethyl silica ethyl vinylbenzene (productive rate: 90.5%) pungency colourless oil liquid.
(2-a), cationic polymerization process, the poly-cinnamic preparation of tert-butyl dimethyl silica ethyl.Tert-butyl dimethyl silica ethyl vinylbenzene, tertiary butyl dimethyl Si propylstyrene are namely that the monomer of cationoid polymerisation is also the monomer of anionoid polymerization.
Cationic polymerization operates in the inert atmosphere glove box with low temperature cold bath.Under-80 ℃ of conditions, the mixed solvent that adds 20mL hexanaphthene/monochloro methane (50/50v/v) in the polymerization bottle of drying, add continuously subsequently initiator TMPCl solution (0.002mol/L), the 3rd component hexahydropyridine solution (1mL, 0.002mol/L), coinitiator TiCl
4(1mL, 0.036mol/L) solution.Initiator, the 3rd component and coinitiator molar ratio are 1.0: 1.0: 18, ageing 15min, then add tert-butyl dimethyl silica ethyl vinylbenzene (2mL) polymerization.The complete rear methyl alcohol termination reaction of using, precipitation, solvent flashing is dried to constant weight, obtains gathering tert-butyl dimethyl silica ethyl vinylbenzene, and the molecular weight of polymkeric substance is 2.32 * 10
4G/mol, molecular weight distribution is 1.3.
(2-b), anionic polymerisation process, the poly-cinnamic preparation of tert-butyl dimethyl silica ethyl
In the 40mL cyclohexane solution, add 2mL tert-butyl dimethyl silica ethyl vinylbenzene and THF (0.5mL), rear n-BuLi (0.015mol/L) at room temperature causes the tert-butyl dimethyl silica ethyl styrene polymerization, follow exothermic phenomenon, after polymerization 60min, methyl alcohol stops, precipitation, and vacuum-drying obtains poly-to tert-butyl dimethyl silica ethyl vinylbenzene.
(3), poly-to the cinnamic hydrolysis of tert-butyl dimethyl silica ethyl
Poly-tert-butyl dimethyl silica ethyl vinylbenzene (1.0g) is dissolved in THF/DMF (50/50v/v) mixed solvent, adds the tetrahydrofuran solution (4mL, 1.0mol/L) of normal-butyl fluoride amine, stirs 30h in inert gas environment.Add a large amount of deionized waters after cooling, precipitation, suction filtration, drying.After the product washing, obtain poly-hydroxyethyl vinylbenzene.
Cationic polymerization process, the preparation of poly-tertiary butyl dimethyl Si propylstyrene; Then, press embodiment 1 (3) method, poly-hydrolysis to the tertiary butyl dimethyl Si propylstyrene is made poly-hydroxyethyl vinylbenzene.
Cationic polymerization operates in the inert atmosphere glove box with low temperature cold bath.Under-80 ℃ of conditions, the mixed solvent that adds 20mL hexanaphthene/monochloro methane (50/50v/v) in the polymerization bottle of drying, add continuously subsequently initiator TMPCl solution (0.002mol/L), the 3rd component hexahydropyridine solution (1mL, 0.002mol/L), coinitiator ethyl aluminum dichloride (1mL, 0.036mol/L) solution.Initiator, the 3rd component and coinitiator molar ratio are 1.0: 1.0: 18, ageing 15min, then add tertiary butyl dimethyl Si propylstyrene (2mL) polymerization.The complete rear methyl alcohol termination reaction of using, precipitation, solvent flashing is dried to constant weight, obtains gathering tert-butyl dimethyl silica ethyl vinylbenzene, and the molecular weight of polymkeric substance is 3.12 * 10
4G/mol, molecular weight distribution is 1.4.
Cationic polymerization process, the preparation of the segmented copolymer of iso-butylene and tertiary butyl dimethyl Si propylstyrene; Then, press embodiment 1 (3) method, the poly-hydrolysis to the tertiary butyl dimethyl Si propylstyrene of iso-butylene-b is made the poly-hydroxypropyl vinylbenzene of polyisobutene-b.
Cationic polymerization operates in the inert atmosphere glove box with low temperature cold bath.Under-80 ℃ of conditions, the mixed solvent that adds 20mL hexanaphthene/monochloro methane (50/50v/v) in the polymerization bottle of drying, wherein tetrahydrofuran (THF) and N, the dinethylformamide volume ratio is 1: 0.1～10, add continuously subsequently initiator TMPCl solution (0.002mol/L), the 3rd component hexahydropyridine solution (1mL, 0.002mol/L), coinitiator ethyl aluminum dichloride (1mL, 0.036mol/L) solution.Initiator, the 3rd component and coinitiator molar ratio are 1.0: 1.0: 18, ageing 15min, add again iso-butylene (2mL), after polymerization 40 minutes, add tertiary butyl dimethyl Si propylstyrene (2mL) polymerization, iso-butylene and tertiary butyl dimethyl Si propylstyrene mass ratio are 0.88: 0.5 again).The complete rear methyl alcohol termination reaction of using, precipitation, solvent flashing is dried to constant weight, obtains polyisobutene-b-poly-to the tert-butyl dimethyl silica ethyl styrene block copolymer, and the molecular weight of polymkeric substance is 5.05 * 10
4G/mol, molecular weight distribution is 1.4.
Claims (5)
1. side group contains the polymkeric substance of hydroxy styrenes, it is characterized in that: take tert-butyl dimethyl silica ethyl vinylbenzene or tertiary butyl dimethyl Si propylstyrene as monomer, by sun/anionoid polymerization preparation, comprise that side group contains homopolymer and the segmented copolymer of hydroxy styrenes
The homopolymer that side group contains hydroxy styrenes refers to poly-hydroxyethyl vinylbenzene or the poly-hydroxypropyl vinylbenzene take tert-butyl dimethyl silica ethyl vinylbenzene or tertiary butyl dimethyl Si propylstyrene as the monomer preparation, each structural unit of homopolymer contains hydroxyl, the number-average molecular weight scope is 2000～200000g/mol, and molecular weight distribution is between 1.1～5.0;
The segmented copolymer that side group contains hydroxy styrenes refers to by after a kind of monomer generation copolymerization in tert-butyl dimethyl silica ethyl vinylbenzene or tertiary butyl dimethyl Si propylstyrene and iso-butylene, isoprene and divinyl, hydrolysis obtains segmented copolymer again, contain the hydroxyl polystyrene and partly account for whole molecular chain 10～40% mass percents, segmented copolymer number-average molecular weight scope is 20000～500000g/mol, and molecular weight distribution is between 1.1～5.0.
2. side group according to claim 1 contains the polymkeric substance of hydroxy styrenes, and segmented copolymer specifically refers to by hydrolysis tert-butyl dimethyl silica ethyl vinylbenzene and isobutylene copolymers, tert-butyl dimethyl silica ethyl vinylbenzene and isoprene copolymer, tert-butyl dimethyl silica ethyl vinylbenzene and butadienecopolymer, tertiary butyl dimethyl Si propylstyrene and with isobutylene copolymers, tertiary butyl dimethyl Si propylstyrene and isoprene copolymer and tertiary butyl dimethyl Si propylstyrene and butadienecopolymer and obtains.
3. side group claimed in claim 1 contains the preparation method of the polymkeric substance of hydroxy styrenes, it is characterized in that: the preparation method was divided into for three steps:
(1) tert-butyl dimethyl silica ethyl vinylbenzene and tertiary butyl dimethyl Si propylstyrene is synthetic: wherein
Tert-butyl dimethyl silica ethyl vinylbenzene synthetic route:
Take the 4-bromstyrol as raw material, temperature of reaction is the 0-70 degree, generates 4-(2-hydroxyethyl) vinylbenzene by Grignard reagent and reacting ethylene oxide; Due in the anion/cation polymerization process, hydroxyl can participate in chain termination reaction, therefore, hydroxyl protection must be got up before polymerization, by TERT-BUTYL DIMETHYL CHLORO SILANE, hydroxyl is protected, imidazoles is catalyzer, prepares tert-butyl dimethyl silica ethyl vinylbenzene after reaction, and wherein the molar ratio between magnesium, 4-bromstyrol and oxyethane is 1: 0.8～1.2: 1.0～4.0; Molar ratio 1: 1.0～2.0: 1.0～2.0 between 4-(2-hydroxyethyl) vinylbenzene, TERT-BUTYL DIMETHYL CHLORO SILANE and imidazoles;
Tert-butyl dimethyl silica ethyl vinylbenzene: the pungency colourless oil liquid, boiling point: 98 ℃, 1～2mb, density is: 1.205g/cm
3
The synthetic route of tertiary butyl dimethyl Si propylstyrene:
Take the 4-bromstyrol as raw material, temperature of reaction is the 0-70 degree, generate 4-(3-hydroxypropyl) vinylbenzene by Grignard reagent and propylene oxide reaction, then by TERT-BUTYL DIMETHYL CHLORO SILANE, hydroxyl is protected, imidazoles is catalyzer, prepares the tertiary butyl dimethyl Si propylstyrene after reaction; Wherein the molar ratio between magnesium, 4-bromstyrol and propylene oxide is 1: 0.8～1.2: 1.0～4.0; Molar ratio 1: 1.0～2.0: 1.0～2.0 between 4-(2-hydroxypropyl) vinylbenzene, TERT-BUTYL DIMETHYL CHLORO SILANE and imidazoles;
The tertiary butyl dimethyl Si propylstyrene: the pungency colourless oil liquid, boiling point: 105 ℃, 1～2mb, density is: 1.255g/cm
3
(2) homopolymer and the Synthesis of copolymer take tert-butyl dimethyl silica ethyl vinylbenzene or tertiary butyl dimethyl Si propylstyrene as monomer:
The poly-tert-butyl dimethyl silica ethyl vinylbenzene of cationoid polymerisation preparation and poly-tertiary butyl dimethyl Si propylstyrene homopolymer:
in cationoid polymerisation, under cold condition, 0～-100 ℃, with methyl chloride or methyl chloride and mixed alkane solvent, methyl chloride and alkane volume ratio are 1.0: 0.1～5.0, add initiator respectively in mixed solvent again, the 3rd component and coinitiator, initiator concentration is: 1mol/L～10-5mol/L, coinitiator concentration is 10mol/L～10-4mol/L, the 3rd concentration of component is: 0.1mol/L～10-6mol/L, initiator, the 3rd component and coinitiator molar ratio are 1.0: 0.1～10: 1.0～60, add subsequently above-mentioned monomer tert-butyl dimethyl silica ethyl vinylbenzene or tertiary butyl dimethyl Si propylstyrene to prepare homopolymer, polymerization time is 30 minutes～24 hours, monomer concentration 0.5mol/L～20mol/L wherein, polymkeric substance are at last by methanol extraction, washing, drying, the number-average molecular weight scope of homopolymer is 2000～200000g/mol, and molecular weight distribution is between 1.1～5.0,
The cationoid polymerisation route of poly-tertiary butyl dimethyl Si propylstyrene:
The poly-tert-butyl dimethyl silica ethyl vinylbenzene of cationoid polymerisation preparation and poly-tertiary butyl dimethyl Si propylstyrene multipolymer:
In cationoid polymerisation, under cold condition, 0～-100 ℃, with methyl chloride or methyl chloride and mixed alkane solvent, methyl chloride and alkane volume ratio are 1.0: 0.1～5.0, then add initiator, the 3rd component and coinitiator respectively in mixed solvent, and initiator concentration is: 1mol/L～10
-5Mol/L, coinitiator concentration is 10mol/L～10
-4Mol/L, the 3rd concentration of component is: 0.1mol/L～10
-6Mol/L, initiator, the 3rd component and coinitiator molar ratio are 1.0: 0.1～10: 1.0～60, the mode that sequentially adds subsequently pan feeding first added isobutene polymerisation 30～2 hours, add tert-butyl dimethyl silica ethyl vinylbenzene or tertiary butyl dimethyl Si propylstyrene, the repolymerization time is 30 minutes～24 hours again; Monomer concentration 0.5mol/L～20mol/L wherein, iso-butylene and tert-butyl dimethyl silica ethyl vinylbenzene or with the mass ratio of tertiary butyl dimethyl Si propylstyrene charging capacity be 0.5～50: 0.5; Polymkeric substance is at last by methanol extraction, washing, drying; The number-average molecular weight scope of multipolymer polymers is 2000～200000g/mol, and molecular weight distribution is between 1.1～5.0;
The poly-tert-butyl dimethyl silica ethyl vinylbenzene of anionoid polymerization preparation or poly-tertiary butyl dimethyl Si propylstyrene homopolymer:
In anionoid polymerization, take alkane as solvent, butyllithium is initiator, and initiator concentration is 1mol/L～l0
-5Mol/L, above-mentioned monomer tert-butyl dimethyl silica ethyl vinylbenzene or tertiary butyl dimethyl Si propylstyrene prepare homopolymer; Polymerization time 1～20 hour; Homopolymer or multipolymer pass through methanol extraction, washing, final drying, and the number-average molecular weight scope of homopolymer is 2000～200000g/mol, molecular weight distribution is between 1.1～5.0;
The poly-tert-butyl dimethyl silica ethyl vinylbenzene of anionoid polymerization preparation and poly-tertiary butyl dimethyl Si propylstyrene multipolymer:
In anionoid polymerization, take alkane as solvent, butyllithium is initiator, and initiator concentration is 1mol/L～l0
-5Mol/L adds the mode of pan feeding by order, first add tert-butyl dimethyl silica ethyl vinylbenzene or tertiary butyl dimethyl Si propylstyrene, then add isoprene or divinyl to prepare segmented copolymer, polymerization time 1～20 hour; The mass ratio of isoprene or divinyl and tert-butyl dimethyl silica ethyl vinylbenzene or tertiary butyl dimethyl Si propylstyrene charging capacity is 0.5～50: 0.5, multipolymer is by methanol extraction, washing, final drying, the number-average molecular weight scope of multipolymer polymers is 2000～200000g/mol, and molecular weight distribution is between 1.1～5.0;
(3) side group contains the hydrolysis preparation of the polymkeric substance of hydroxy styrenes: preparing the hydrolysis of homopolymer and multipolymer by sun/anionoid polymerization as monomer at tetrahydrofuran (THF) and N take tert-butyl dimethyl silica ethyl vinylbenzene or tertiary butyl dimethyl Si propylstyrene, in the mixed solvent of dinethylformamide, wherein tetrahydrofuran (THF) and N, the dinethylformamide volume ratio is 1: 0.1～10, under the effect of n-butyl ammonium fluoride, deviate from blocking group, generating side group is polystyrene homopolymer or the segmented copolymer of hydroxyethyl and hydroxypropyl, n-butyl ammonium fluoride concentration is 0.02～2mol/L.
4. side group according to claim 3 contains the preparation method of the polymkeric substance of hydroxy styrenes, it is characterized in that: in cationoid polymerisation:
Described initiator is 2-chloro-2,4, a kind of in 4-trimethylpentane TMPCl or water;
Described the 3rd component is a kind of in hexahydropyridine or 2,6-di-tert-butyl pyridine;
Described coinitiator is a kind of in titanium tetrachloride, aluminum chloride, a chloroethyl aluminium and ethyl aluminum dichloride.
5. contained the purposes of the polymkeric substance of hydroxy styrenes by the side group described in claim 1, be used for timbering material, cartilage material, Thermosensitive Material Used for Controlled Releasing of Medicine and vascular grafts.
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