CN107337772A - A kind of preparation method of hydroxyl styrene copolymer - Google Patents

A kind of preparation method of hydroxyl styrene copolymer Download PDF

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CN107337772A
CN107337772A CN201710652437.7A CN201710652437A CN107337772A CN 107337772 A CN107337772 A CN 107337772A CN 201710652437 A CN201710652437 A CN 201710652437A CN 107337772 A CN107337772 A CN 107337772A
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copolymer
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styrene
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solvent
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CN107337772B (en
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张爱民
徐雨
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Sichuan University
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Sichuan University
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C08F297/048—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes polymerising vinyl aromatic monomers, conjugated dienes and polar monomers

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Abstract

The invention discloses a kind of preparation method of hydroxyl styrene copolymer.The present invention uses specific feature comonomer, prepares styrene copolymer by cationic polymerization or anionic polymerisation, then obtain hydroxyl styrene copolymer by hydrolysis.The ion polymerization preparation time that the present invention uses is short, quick and high efficient reaction, prepared hydroxyl styrene copolymer the advantages of to have that molecular weight is high, hydroxyl structure unit is adjustable controllable, is especially suitable for industrialized production.

Description

A kind of preparation method of hydroxyl styrene copolymer
Technical field
The invention belongs to styrene copolymer, and in particular to a kind of preparation side of hydroxyl styrene copolymer Method.
Background technology
Styrene copolymer is a kind of polymeric material that polystyrene chain segment in strand be present, such as polyphenyl second Alkene/Butadiene/Styrene block copolymer (SBS), styrene/ethylene-butylene/styrene block copolymer (SEBS), polyphenyl Ethene/isoprene/styrene block copolymer (SIS), polystyrene/isoprene/styrene block copolymer (SIS), Polystyrene/ethylene-propylene/styrene block copolymer (SEPS), polystyrene/Ethylene-Propylene Block Copolymer (SEP) Deng.Exist in these material matrix and the phase region formed is mutually run through by strand soft segment and hard section, soft, hard segment is distinguished under normal temperature In viscous state, glassy state, but high resiliency is presented in hard section limitation soft segment flowing, material；Soft under high temperature, hard segment is in viscosity flow Thermoplasticity is integrally presented in state, material, and this characteristic causes them to be commonly used for preparing blending and modifying PP Pipe Compound.Wherein, electric wire electricity Cable coated insulation material, solid tire of bicycle are exactly one of its widest application.
Styrene copolymer as wire cable material, solid tyre, it is necessary to have good solvent resistance.Styrene Analog copolymer is nonpolar linear macromolecule, and resistance to dissolubility is poor, runs into gasoline, toluene, hexamethylene equal solvent, then quick dissolving, Mechanical property significantly declines, and can not use.It is well known that molecule interchain linkage is to improve the best side of polymer solvent resistance Method, but there is no active group on described styrene copolymer strand, molecule interchain can not form cross-bond.At present, have The report of some methods being modified on styrene copolymer, such as sulfonation ((Synthesis and characterization of sulfonated poly(styrene-b-(ethylene-ran-butylene)-b- styrene)/(strontium titanate)nanocomposites.European Polymer Journal,2013,49: 1446), acetylation, carboxylation (Synthesis of novel triblock copolymers containing hydrogen- bond interaction groups via chemical modification of hydrogenated poly (styrene-block-butadiene-block-styrene).Macromolecules,1995,28:8702), chloromethylation (Studies on performing chloromethylation reaction for polystyrene by micellar catalysis in aqueous surfactant solutions.Chemical Engineering and Processing,2008,47:852), maleic anhydride grafting (Improved compatibility between polyamide and polypropylene by the use of maleic anhydride grafted SEBS.Polymer,1998, 39:6705) etc..Wherein, more, the modified styrenics copolymerization of gained is reported the methods of sulfonation, acetylation, maleic anhydride grafting Though connecting polar group on thing strand, there is no reactivity, can not be with other activated monomers or polymer reaction.Chloromethyl The chloromethyl changed on styrol copolymer strand has reactivity, can further be modified and be met the poly- of various applications Compound, but course of reaction is complicated, it is with high costs.Hydroxyl on the strand of hydroxystyre-ne copolymer, reactivity are high, can be with Participate in cross-linking reaction.It is poly- to hydroxyl that Maruzen oil companies once used free radical polymerisation process to be prepared using vinylphenol as monomer Base styrene (US 4028340), Hoechst Celanese companies with same procedure using to acetoxy-styrene as monomer system Standby polycarboxylated styrene (US 5264528), the molecular weight of both products therefroms is all wider, and last handling process is complicated.
Compared to traditional free crowd method, the suitable monomers scope of Transfer Radical Polymerization (ATRP) is wide, polymerization The characteristics of mild condition, strong MOLECULE DESIGN ability.Patent CA105924553A reports prepares narrow molecular weight distribution using ATRP Polyhydroxystyrene polymer, but described polymerization polymerization time is up to 18-22 hours, and products therefrom molecular weight No more than 1.5 ten thousand, the heavy metal in product is also required to remove.For industrialized production, production efficiency is low, and is produced into This is high.In addition, have no the report that hydroxyl styrol copolymer is prepared using this method.As can be seen here, high efficiency, quick system Standby molecular weight height, narrow molecular weight distribution, the hydroxyl styrene copolymer of molecule segment structure-controllable is still one has The work of challenge.
At present, there is not the report that hydroxyl styrene copolymer is prepared using ion polymerization also.
The content of the invention
It is an object of the invention to provide a kind of preparation method of hydroxyl styrene copolymer.
A kind of preparation method of hydroxyl styrene copolymer, it comprises the following steps：
(1) monomer containing Formulas I and/or Formula II structure is gathered with other vinyl monomers by anionic polymerisation or cation Conjunction prepares copolymer；
(2) copolymer obtained by step (1) is dissolved into solvent and forms copolymer solution, then mixed with buck, in 30~ 1~12h is hydrolyzed at 100 DEG C, copolymer is settled out, hydroxyl styrene copolymer is produced after drying；
Wherein, R1、R2Separately it is selected from C1~12Alkyl, C1~12Cycloalkyl, C6~12Aryl, C1~12Heterocyclic aryl, C1~12 Heterocyclylalkyl, wherein the alkyl, cycloalkyl, aryl, heterocyclic aryl, Heterocyclylalkyl further can be independently selected from by 1~4 C1~6Alkyl, C1~6Cycloalkyl, C1~6Alkoxy, C1~6Alkylamino radical, C1~6Carbalkoxy, C1~6The substituent substitution of alkanoyl；
Other described vinyl monomers are in the alkene for can be carried out with styrene monomer anion or cationic polymerization It is one or more；
Described anionic polymerisation comprises the following steps：With Multistep feeding or disposable feed way, will have Formulas I and/ Or the monomer of structure shown in Formula II and other vinyl monomers be added to containing activator, solvent system in be well mixed, then Initiator polyase 13 0~180 minute at 25~90 DEG C is added, is hydrogenated or not hydrogenated after reaction terminating, finally removed molten Agent, obtain the copolymer containing Formulas I and/or Formula II construction unit；
Wherein, the activator described in anionic polymerisation is polar compounds oxygen-containing and/or nitrogenous but without reactive hydrogen Thing, solvent are any solvent that can dissolve the monomer simultaneously, and initiator is alkyl metal cpd, alkoxide compound In any one.
Described cationic polymerization comprises the following steps：With Multistep feeding or disposable feed way, will have Formulas I and/ Or the monomer of structure shown in Formula II and other vinyl monomers are added in halogenated hydrocarbons and/or alkane solvent and are well mixed, and reduce temperature Degree adds Lewis acid initiators to less than 0 DEG C, and polymerization time was hydrogenated or not hydrogen no more than 1 hour after reaction terminating Change, finally obtain the copolymer containing Formulas I and/or Formula II construction unit.
Further, the R1、R2Separately it is selected from C1~8Alkyl, C1~8Cycloalkyl, C6~8Aryl, C1~8Heterocycle virtue Base, C1~8Heterocyclylalkyl；Preferably, the R1、R2Separately selected from methyl, ethyl, propyl group, isopropyl.
Further, other described vinyl monomers are styrene, α-methylstyrene, isobutene, 3- methyl isophthalic acids-fourth One or more in alkene, 4-methyl-1-pentene, butadiene, 1,3- pentadienes, isoprene.
Further, in step (1), the mass fraction N with the monomer of structure shown in Formulas I and/or Formula II is 0<N ≤ 33%, preferably 3≤N≤25%.
Further, in the anionic polymerisation, the mass concentration of monomer is no more than 15% in reaction system；And/or Design under molecular weight, initiator mole dosage is 1~1.25 times of theoretical amount；And/or the mol ratio of initiator and activator For 1:0.02~20, preferably 1：0.07~17.
Further, in the anionic polymerisation, activator is tetrahydrofuran, dioxane, tetrahydrofurfuryl alcohol ethylether, N, One or more in N- dimethyl tetrahydro chaffs amine, dimethylformamide；And/or solvent is hexamethylene；And/or initiator is Any one in n-BuLi, s-butyl lithium, tert-butyl lithium.
Further, in the cationic polymerization, the mass concentration of monomer is no more than 15% in reaction system；And/or Design under molecular weight, the initiator mole dosage is 1-1.5 times of theoretical amount.
Further, in the cationic polymerization, solvent is in monochloro methane, dichloromethane, dichloroethanes, n-hexane It is one or more；And/or initiator be alchlor, ethyl aluminum dichloride, aluminium diethyl monochloride, triethyl aluminum, butter of tin, Any one in titanium tetrachloride.
Further, in step (2), the copolymer solution mass concentration is no more than 15%；And/or the solvent is It is any to dissolve the copolymer containing Formulas I and/or Formula II construction unit and the not solvent with buck reaction；And/or copolymer is molten The mass ratio of liquid and buck is 100~20:1；And/or described aqueous alkali is by alkali metal hydroxide, phase transfer catalyst Formed with water；The mass concentration ω of alkali metal hydroxide scope is 0<ω≤55%；The mass concentration δ of phase transfer catalyst Scope be 0<δ≤15%.
Further, in step (2), the solvent is hexamethylene, n-hexane, normal heptane, normal octane, toluene, dimethylbenzene In any one；And/or the alkali metal hydroxide is any one in lithium hydroxide, potassium hydroxide, sodium hydroxide Kind, and mass concentration ω scope is 25≤ω≤50%；And/or the phase transfer catalyst is quaternary ammonium salt, alkyl halide Any one in ammonium, tertiary amines, quaternary ammonium bases, quaternary phosphonium salt class, cyclic crown ether class, and the model of the mass concentration δ in buck Enclose for 5≤δ≤15%；Preferably, phase transfer catalyst is alkyl ammonium halide class.
Present invention also offers a kind of hydroxyl styrene copolymer, and it is prepared with above-mentioned preparation method.
The minimum value of carbon content and maximum are represented by prefix in hydrocarbon group, for example, prefix Ca-bAlkyl, Ca-b Cycloalkyl, Ca-bAryl, Ca-bHeterocyclic aryl, Ca-bHeterocyclylalkyl represents any and contains alkyl, the ring of " a " to " b " individual carbon atom respectively Alkyl, aryl, heterocyclic aryl, Heterocyclylalkyl and its substituent.For example, C1-4Alkyl refers to the alkyl for including 1~4 carbon atom, C8Aryl includes xylyl, ethylbenzene.
Ca-bAlkoxy, Ca-bCarbalkoxy, Ca-bAlkylamino, Ca-bAcyl group refers respectively to the alkane to " b " individual carbon atom containing " a " Base and corresponding oxygen atom, ester group, amino, the connected obtained group of acyl group.
The present invention be inventor by experimental study repeatedly, obtained a kind of hydroxyl styrene copolymer.
The invention discloses a kind of brand-new method for preparing hydroxyl styrene copolymer.The present invention is preparing benzene In the polymerization process of ethene copolymer, feature comonomer is added, compared with prior art, hydroxy styrenes is simplified and is total to The preparation process of polymers, post processing is simple, quick and high efficient reaction, prepared hydroxyl styrene copolymer elastomer tool Have molecular weight height, narrow molecular weight distribution, hydroxyl structure unit is adjustable it is controllable the advantages of, be especially suitable for industrialized production.
Obviously, according to the above of the present invention, according to the ordinary technical knowledge and customary means of this area, do not departing from Under the premise of the above-mentioned basic fundamental thought of the present invention, the modification, replacement or change of other diversified forms can also be made.
Brief description of the drawings
The FTIR spectrum of styrene copolymer (sample 1-2) hydroxyl Fig. 1.
Styrene copolymer (sample 1-2) hydroxyl Fig. 21H NMR scheme.
Embodiment
The embodiment of form by the following examples, the above of the present invention is remake further specifically It is bright.But the scope that this should not be interpreted as to the above-mentioned theme of the present invention is only limitted to following example.It is all to be based on the above of the present invention The technology realized belongs to the scope of the present invention.
Reagent used in the embodiment of the present invention mainly has：4- ethylene benzyls acetic acid esters, to 4- acetoxy-styrenes, positive fourth Base lithium (1.6M), styrene, furfuryl alcohol, methyl diphenylene diisocyanate are purchased in Adamas Reagent Companies；Alchlor, two Chloroethyl aluminium, aluminium diethyl monochloride, furans acyl chlorides, chaff amine are purchased in Aladdin Reagent Companies；Butter of tin (1M) purchase in Acros Reagent Companies, toluene di-isocyanate(TDI) are purchased in TCI Reagent Companies, are conventional commercial product.
With CDCl3As solvent, obtained copolymer is carried out with Bruker AV 600MHz NMRs1HNMR Test.
Using chloroform as solvent, on KBr salt pieces after film, using Nieolet NEXUS670 Fourier infrared spectrograph devices Carry out infrared test.
The anionic polymerisation of embodiment 1 prepares hydroxyl styrene-ethylene/butylene-styrene linear block copolymers
1L polymeric kettles are vacuumized, with high pure nitrogen displacement three times, first add the hexamethylene of 650ml purifying, design contains admittedly Amount 10%, match and feed by Tables 1 and 2, first add first paragraph to 4- ethylene benzyls acetic acid esters and styrene mix monomer, 0.25ml (3mmol) tetrahydrofuran, opens stirring, by table 2 match add n-BuLi cyclohexane solution (concentration 0.5M), 40 DEG C It is lower reaction 1 hour, then add butadiene, continue reaction 1 hour, finally add the 3rd section 4- ethylene benzyls acetic acid esters and Styrene mix monomer, then react 1 hour.After reaction terminates, polymeric liquid is pressed into hydrogenation kettle, is passed through hydrogen terminating reaction. After half an hour, it is 0.02mol/L o-methyl benzoic acid methyl esters to add 1mL concentration, 30mg catalyst cyclopentadienyl titanium dichlorides, then is passed through hydrogen Gas, control temperature 70 C, pressure 2MPa, reaction discharge after terminating 6 hours.
The mol ratio of mix monomer in the embodiment 1 of table 1
Into product mixture, it is 50wt% sodium hydroxide aqueous alkalis to add 10ml concentration, contains 5wt% in aqueous alkali TBAB, hydrolyzed 3 hours in 60 DEG C, add methanol in most backward reaction solution, precipitate product, and dried, that is, obtained Hydroxyl styrene-ethylene/butylene-styrene block copolymer.Its synthesizing formula and technique and molecule measuring test result 2 are shown in Table, infrared spectrum is shown in Fig. 1,1H NMR are shown in Fig. 2.
The synthesizing formula of the hydroxyl styrene-ethylene/butylene-styrene linear block copolymers of table 2
Fig. 1 and Fig. 2 be respectively sample 1-2 hydroxyl styrene copolymer FTIR spectrum and1H NMR Figure, from figure it was found from result, the present invention prepares hydroxyl styrol copolymer.With reference to the result of table 2, the present invention passes through regulation The content of hydroxyl in monomer, it can prepare with different hydroxy radical contents, different molecular weight, the styrene of narrow molecular weight distribution- Ethylene/butylene-styrene block copolymer.
Wherein, SBC molecular weight is less than less than 50,000, and mechanical property is poor, and moieties amount is less than 2 Ten thousand product is high viscosity liquid, and use range is limited.
The anionic polymerisation of embodiment 2 prepares the star-like styrene-ethylene/butylene-styrene block copolymer of hydroxyl
By the raw material proportioning and technique of 1-5,1-6 and 1-7 in table 1, the acetic acid esters construction unit of ethylene benzyl containing 4- is synthesized Linear styrene-butadiene-styrene linear block copolymers, after adding the 3rd section of reaction monomers and reacting 1 hour, by thing Material press-in hydrogenation kettle, is formulated by table 3, adds coupling agent, and 40 DEG C are continued to react 30min, obtain the acetic acid esters knot of ethylene benzyl containing 4- The star-like SBS glue of structure unit.React after terminating according to the method hydrogen of embodiment 1 Change is handled, and is settled out product and is dried, obtains star-like styrene-ethylene/butylene-benzene of 4- ethylene benzyl acetic acid esters construction units Ethylene block copolymer glue.
Product is dissolved in normal octane and forms solution, it is 40wt% sodium hydroxide aqueous alkalis to add 50ml concentration, buck In cetyl trimethylammonium bromide containing 5wt%, hydrolyzed 1 hour in 70 DEG C, then reaction solution be slowly injected into 100 DEG C of concentration and is Glue, desolvation and other impurities are boiled in 10% sodium hydroxide boiling water, are settled out product, dries, that is, obtains hydroxylated star-like Styrene-ethylene/butylene-styrene block copolymer.
The synthesizing formula and molecule measuring of the hydroxylated star-like styrene-ethylene/butylene-styrene block copolymer of table 3 Test result
When preparing molecular weight and being higher than 500,000 copolymer, the dosage of initiator is few, this purity requirement pole to monomer Height, the control difficulty of molecular weight of product is very big, it is therefore preferable that molecular weight is 50,000~500,000.
The anionic polymerisation of embodiment 3 prepares hydroxyl styrene-ethylene/propylene-styrene block copolymer
1L polymeric kettles are vacuumized, with high pure nitrogen displacement three times, first add the hexamethylene of 650ml purifying, design contains admittedly Amount 15%, by table 4 and the formula charging of table 5.First add first paragraph to 4- acetoxy-styrenes and styrene mix monomer, 1g Tetrahydrofurfuryl alcohol ethylether, stirring is opened, add tert .-butyllithium solution (concentration 0.5M), react 50min at 60 DEG C, then heat to 70 DEG C of addition isoprene, continue reaction 1 hour, finally add the 3rd section and 4- acetoxy-styrenes and styrene are mixed Monomer is closed, then is reacted 1 hour.After reaction terminates, polymeric liquid is pressed into hydrogenation kettle, is passed through hydrogen terminating reaction.After half an hour, 30mg catalyst (nickel naphthenate/triisobutyl aluminium, n (A) l:N (Ni)=5:1), then hydrogen is passed through, controls temperature 50 C, pressure 0.5MPa, discharging, precipitation, filtering after reaction terminates.
The mol ratio of mix monomer in the embodiment 3 of table 4
Product is dissolved in normal heptane or n-hexane, it is 30wt% sodium hydroxide aqueous alkalis to add 50ml concentration, in buck TBAB containing 15wt%, hydrolyzed 3 hours in 60 DEG C, add methanol in most backward reaction solution, precipitate product, and dry It is dry, that is, obtain hydroxyl styrene-ethylene/propylene-styrene block copolymer.Its synthesizing formula and technique and molecular weight Test result is shown in Table 5.
The synthesizing formula of the hydroxyl styrene-ethylene of table 5/propylene-styrene block copolymer
The anionic polymerisation of embodiment 4 prepares hydroxyl styrene-α-methylstyrene-butadiene random copolymer
100ml chloroforms, 0.1mol 4- ethenylphenyl methanol, 0.1mol cyclopenta formyls are added into 500ml flasks Chlorine, 0.6g DMAPs, 8g pyridines, react 12 hours at 20 DEG C.Reaction adds distilled water after terminating, and waits to be layered, takes Organic layer is evaporated under reduced pressure with distillation water washing 5 times, last 50 DEG C repeatedly, is removed chloroform and water, is obtained to 4- ethylene benzyl rings Pentylformic acid ester.
1L polymeric kettles are vacuumized, with high pure nitrogen displacement three times, first add the hexamethylene of 650ml purifying, design contains admittedly Amount 10%.Sequentially add to 11.6g 4- ethylene benzyl cyclopenta formic acid esters (accounting for monomer molar content 7.1%), 4.17g benzene second Alkene, 1.2g α-methylstyrenes, 0.59mol butadiene, 0.234mmol N, N- dimethyl tetrahydro chaff amine, open stirring, add 2.08ml Sec-Butyllithium solutions (concentration 0.5M), react at 60 DEG C 2 hours, finally reaction solution is pressed into and terminated in kettle, adds second Alcohol terminating reaction.
Into product mixture, it is 40wt% sodium hydroxide aqueous alkalis to add 15ml concentration, contains 5wt% 12 in buck Alkyl trimethyl ammonium bromide, hydrolyzed 2 hours in 80 DEG C, add methanol in most backward reaction solution, precipitate product, and dried, i.e., Obtain hydroxyl styrene-α-methylstyrene-butadiene random copolymer, number-average molecular weight about 4.8 ten thousand, molecular weight distribution Width 1.17, the construction unit accounting example 15.4wt% of hydroxyl.
The anionic polymerisation process of embodiment 5 prepares hydroxyl styrene-isoprene random copolymer
The addition 100ml chloroforms into 500ml flasks, 6.71g 4- ethenylphenyl methanol, 8.43g 3- phenylpropyl alcohol acyl chlorides, 0.6g DMAPs, 9g triethylamines, react 9 hours at 25 DEG C.Reaction adds distilled water after terminating, and waits to be layered, has taken Organic layer is evaporated under reduced pressure with distillation water washing 5 times, last 50 DEG C repeatedly, is removed chloroform and water, is obtained to 4- ethylene benzyls (3- Phenyl) propionic ester.
1L polymeric kettles are vacuumized, with high pure nitrogen displacement three times, first add the hexamethylene of 650ml purifying, design contains admittedly Amount 10%.Sequentially add to 13.31g to 4- ethylene benzyls (3- phenyl) propionic ester (accounting for monomer molar content 9.0%), 5.2g benzene Ethene, 31g isoprene, 0.30mmol dimethylformamides, open stirring, add 1.66ml n-butyllithium solution (concentration 0.5M), react at 40 DEG C 3 hours, finally reaction solution is pressed into and terminated in kettle, adds ethanol terminating reaction.
Into product mixture, it is 36wt% sodium hydroxide aqueous alkalis to add 15ml concentration, benzyl containing 8wt% in buck Triethylammonium bromide, hydrolyzed 10 hours in 45 DEG C, add methanol in most backward reaction solution, precipitate product, and dried, that is, obtained Hydroxyl styrene-isoprene random copolymer, number-average molecular weight about 5.9 ten thousand, molecular weight distribution width 1.12, hydroxyl Construction unit accounting example 15.64wt%.
The cationic polymerization process of embodiment 6 prepares hydroxyl styreneisobutylene random copolymer
Solid content 8% is controlled, 500g monochloro methanes (being cooled to -60 DEG C in advance), 7.81g benzene second are sequentially added into 1L polymeric kettles Alkene, 4.4g are opened and are uniformly mixed to 4- ethylene benzyls acetic acid esters (accounting for monomer molar content 4.2%), 27.8g isobutenes, and It is cooled to -80 DEG C or so.Start to be slowly added dropwise the hexane solution of 20ml ethyl aluminum dichlorides containing 12.8mmol/L into reactor, And maintain polymerization temperature.Continue reaction 15 minutes after being added dropwise to complete, what then addition 2ml was precooled contains 0.125mol/L hydrogen-oxygens The ethanol solution for changing sodium terminates polymerization, removes reaction dissolvent and washes, dries, obtains the acetic acid esters construction unit of ethylene benzyl containing 4- Styreneisobutylene random copolymer.
Product is dissolved in 1L toluene, it is 45wt% potassium hydroxide aqueous alkalis to add 30ml concentration, contains 5wt% in buck Tetrabutylammonium chloride, hydrolyzed 8 hours in 50 DEG C, methanol is added in most backward reaction solution, make product precipitation, washing, and dried, i.e., Obtain hydroxyl styreneisobutylene random copolymer, molecular weight 16.2 ten thousand, molecular weight distribution width 5.6, the knot of hydroxyl Structure unit accounting example 8.6wt%.
The cationic polymerization process of embodiment 7 prepares hydroxyl styrene-isoprene random copolymer
It is 8% to control solid content, according to the method for embodiment 6, reaction dissolvent be n-hexane, 7.81g styrene, 4.4g pairs 4- ethylene benzyls acetic acid esters (accounting for monomer molar content 4.2%), 27.8g isoprene, reaction temperature is -30 DEG C, initiator is The dichloromethane solution of 5.5ml 50mmol/L titanium tetrachlorides, in 45 minutes reaction time, other conditions are identical, then hydrolyze, and obtain Hydroxyl styrene-isoprene random copolymer, molecular weight 15.9 ten thousand, molecular weight distribution width 6.2, the structure of hydroxyl Unit accounting example 8.6wt%.
The cationic polymerization process of embodiment 8 prepares hydroxyl styreneisobutylene -3-methyl-1-butene random copolymerization Thing
Solid content 10% is controlled, 500g monochloro methanes (being cooled to -80 DEG C in advance), 15g are sequentially added into 1L polymeric kettles to 4- Ethylene benzyl acetic acid esters (accounting for monomer molar content 12%), 35g mol ratios are 20:1 isobutene/3 methyl isophthalic acids-butylene mixing Thing, open and be uniformly mixed, and be cooled to -100 DEG C or so.Start 11ml is slowly added dropwise into reactor and contain 19.5mmol/L tri- The dichloromethane solution of aluminium chloride, and maintain polymerization temperature.Continue reaction 12 minutes after being added dropwise to complete, then add 3ml precoolings The methanol solution containing 0.125mol/L sodium hydroxides crossed terminates polymerization, removes reaction dissolvent and washes, dries, obtains containing 4- Ethylene benzyl acetic acid esters-isobutene -3-methyl-1-butene random copolymer.
Product is dissolved in 1L dimethylbenzene, it is 25wt% potassium hydroxide aqueous alkalis to add 40ml concentration, is contained in buck 5wt% TTABs, hydrolyzed 12 hours in 35 DEG C, methanol is added in most backward reaction solution, precipitate product, Washing, and is dried, that is, obtains hydroxyl styreneisobutylene -3-methyl-1-butene random copolymer, molecular weight 26.6 ten thousand, Molecular weight distribution width 4.5, the construction unit accounting example 24wt% of hydroxyl.
The cationic polymerization process of embodiment 9 prepares hydroxyl styreneisobutylene -4-methyl-1-pentene random copolymerization Thing
Solid content 15% is controlled, 500g dichloromethane (being cooled to -90 DEG C in advance), 8.1g are sequentially added into 1L polymeric kettles to 4- Acetoxy-styrene (accounting for monomer molar content 4.3%), 6.9g styrene, 60g mol ratios are 15:1 isobutene/4- methyl- 1- pentene mixtures, open and are uniformly mixed, and are cooled to -110 DEG C or so.Start 30ml is slowly added dropwise into reactor and contain The hexane solution of 21.3mmol/L aluminium diethyl monochlorides, and maintain polymerization temperature.Continue reaction 20 minutes after being added dropwise to complete, so The precooled methanol solutions containing 0.2mol/L potassium hydroxide of 3ml are added afterwards and terminate polymerization, are removed reaction dissolvent and are washed, do It is dry, obtain containing the styreneisobutylene to 4- acetoxy-styrene construction units -4-methyl-1-pentene random copolymer.
Product is dissolved in 1L hexamethylenes, it is 30wt% sodium hydroxide aqueous alkalis to add 30ml concentration, is contained in buck 5wt% tricaprylmethyl ammonium bromides, hydrolyzed 9 hours in 45 DEG C, ethanol added in most backward reaction solution, make product precipitation, washing, And dry, that is, obtain hydroxyl styreneisobutylene -4-methyl-1-pentene random copolymer, molecular weight 11.8 ten thousand, molecule Measure the dispersion of distribution 4.3, the ratio 8.2wt% of the construction unit of hydroxyl.
The cationic polymerization process of embodiment 10 prepares hydroxyl styreneisobutylene -1,3- pentadiene random copolymers
Solid content 15% is controlled, 500g dichloroethanes (being cooled to -20 DEG C in advance), 9.8g are sequentially added into 1L polymeric kettles to 4- Acetoxy-styrene (accounting for monomer molar content 4.3%), 5.2g styrene, 60g mol ratios are 15:1 isobutene/1,3- penta 2 Alkene mixture, opens and is uniformly mixed.The dichloromethane that 18.75ml butters of tin containing 20mmol/L are injected into reactor is molten Liquid, and maintain polymerization temperature to continue reaction 1 hour, then add the precooled methanol containing 0.2mol/L potassium hydroxide of 3ml Solution terminates polymerization, removes reaction dissolvent and washes, dries, obtains containing the benzene second to 4- acetoxy-styrene construction units Alkene-isobutene -1,3- pentadiene random copolymers.
Product is dissolved in 1L hexamethylenes, it is 50wt% sodium hydroxide aqueous alkalis to add 20ml concentration, is contained in buck 5wt% TBABs, hydrolyzed 12 hours in 30 DEG C, reaction solution is poured into boiling water, is settled out product, obtained after drying Hydroxyl styreneisobutylene -1,3-pentadiene random copolymer, molecular weight 29.2 ten thousand, molecular weight distribution width 3.8, contains The ratio 10.02wt% of the construction unit of hydroxyl.
The present invention uses specific feature comonomer, and phenylethylene is prepared by cationic polymerization or anionic polymerisation Copolymer, then hydroxyl styrene copolymer is obtained by hydrolysis.The ion polymerization preparation time that the present invention uses Short, quick and high efficient reaction, prepared hydroxyl styrene copolymer has molecular weight is high, hydroxyl structure unit is adjustable can The advantages of control, it is especially suitable for industrialized production.

Claims (11)

  1. A kind of 1. preparation method of hydroxyl styrene copolymer, it is characterised in that：It comprises the following steps：
    (1) monomer containing Formulas I and/or Formula II structure passes through anionic polymerisation or cationic polymerization system with other vinyl monomers Standby copolymer；
    (2) copolymer obtained by step (1) is dissolved into solvent and forms copolymer solution, then mixed with buck, in 30~100 DEG C 1~12h of lower hydrolysis, is settled out copolymer, hydroxyl styrene copolymer is produced after drying；
    Wherein, R1、R2Separately it is selected from C1~12Alkyl, C1~12Cycloalkyl, C6~12Aryl, C1~12Heterocyclic aryl, C1 ~12Heterocyclylalkyl, wherein the alkyl, cycloalkyl, aryl, heterocyclic aryl, Heterocyclylalkyl can be further by 1~4 independences Selected from C1~6Alkyl, C1~6Cycloalkyl, C1~6Alkoxy, C1~6Alkylamino radical, C1~6Carbalkoxy, C1~6The substituent of alkanoyl Substitution；
    Other described vinyl monomers are in the olefinic monomer for can be carried out with styrene monomer anion or cationic polymerization It is one or more；
    Described anionic polymerisation comprises the following steps：With Multistep feeding or disposable feed way, will have Formulas I and/or formula The monomer of structure shown in II and other vinyl monomers be added to containing activator, solvent system in be well mixed, add Initiator polyase 13 0~180 minute at 25~90 DEG C, is hydrogenated after reaction terminating or is not hydrogenated, and last desolvation, is obtained To the copolymer containing Formulas I and/or Formula II construction unit；
    Wherein, the activator described in anionic polymerisation is polar compound oxygen-containing and/or nitrogenous but without reactive hydrogen, molten Agent is any solvent that can dissolve monomer simultaneously, and initiator is any in alkyl metal cpd, alkoxide compound It is a kind of；
    Described cationic polymerization comprises the following steps：With Multistep feeding or disposable feed way, will have Formulas I and/or formula The monomer of structure shown in II and other vinyl monomers, which are added in halogenated hydrocarbons and/or alkane solvent, to be well mixed, and reduces temperature to 0 Below DEG C, Lewis acid initiators are added, polymerization time is no more than 1 hour, is hydrogenated or do not hydrogenated after reaction terminating, most The copolymer containing Formulas I and/or Formula II construction unit is obtained afterwards.
  2. 2. preparation method according to claim 1, it is characterised in that：The R1、R2Separately it is selected from C1~8Alkyl, C1~8Cycloalkyl, C6~8Aryl, C1~8Heterocyclic aryl, C1~8Heterocyclylalkyl；Preferably, the R1、R2Separately it is selected from Methyl, ethyl, propyl group, isopropyl.
  3. 3. preparation method according to claim 1, it is characterised in that：Other described vinyl monomers are styrene, α-first One in base styrene, isobutene, 3-methyl-1-butene, 4-methyl-1-pentene, butadiene, 1,3- pentadienes, isoprene Kind is a variety of.
  4. 4. according to any one of claims 1 to 3 preparation method, it is characterised in that：In step (1), it is described have Formulas I and/ Or the mass fraction N of the monomer of structure shown in Formula II is 0<N≤33%, preferably 3≤N≤25%.
  5. 5. preparation method according to claim 1, it is characterised in that：In the anionic polymerisation, monomer in reaction system Mass concentration is no more than 15%；And/or in the case where designing molecular weight, initiator mole dosage is 1~1.25 times of theoretical amount； And/or the mol ratio of initiator and activator is 1:0.02~20, preferably 1：0.07~17.
  6. 6. according to the preparation method of claim 1 or 5, it is characterised in that：In the anionic polymerisation, activator is tetrahydrochysene furan Mutter, dioxane, tetrahydrofurfuryl alcohol ethylether, N, the one or more in N- dimethyl tetrahydro chaffs amine, dimethylformamide；With/ Or, solvent is hexamethylene；And/or initiator is any one in n-BuLi, s-butyl lithium, tert-butyl lithium.
  7. 7. preparation method according to claim 1, it is characterised in that：In the cationic polymerization, monomer in reaction system Mass concentration is no more than 15%；And/or in the case where designing molecular weight, the initiator mole dosage is the 1-1.5 of theoretical amount Times.
  8. 8. according to the preparation method of claim 1 or 7, it is characterised in that：In the cationic polymerization, solvent is a chloromethane One or more in alkane, dichloromethane, dichloroethanes, n-hexane；And/or initiator be alchlor, ethyl aluminum dichloride, Any one in aluminium diethyl monochloride, triethyl aluminum, butter of tin, titanium tetrachloride.
  9. 9. preparation method according to claim 1, it is characterised in that：In step (2), the copolymer solution mass concentration is not More than 15%；And/or the solvent for it is any can dissolve the copolymer containing Formulas I and/or Formula II construction unit and not with buck The solvent of reaction；And/or the mass ratio of copolymer solution and buck is 100~20:1；And/or described aqueous alkali is by alkali Metal hydroxides, phase transfer catalyst and water composition；The mass concentration ω of alkali metal hydroxide scope is 0<ω≤ 55%；The mass concentration δ of phase transfer catalyst scope is 0<δ≤15%.
  10. 10. preparation method according to claim 9, it is characterised in that：In step (2), the solvent be hexamethylene, just oneself Any one in alkane, normal heptane, normal octane, toluene, dimethylbenzene；And/or the alkali metal hydroxide be lithium hydroxide, Any one in potassium hydroxide, sodium hydroxide, and mass concentration ω scope is 25≤ω≤50%；And/or the phase turns Shifting catalyst is any one in quaternary ammonium salt, alkyl ammonium halide, tertiary amines, quaternary ammonium bases, quaternary phosphonium salt class, cyclic crown ether class, And the scope of the mass concentration δ in buck is 5≤δ≤15%；Preferably, phase transfer catalyst is alkyl ammonium halide class.
  11. A kind of 11. hydroxyl styrene copolymer, it is characterised in that：It is with any one of claim 1~10 system Preparation Method is prepared.
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