CN102603942B - Two-phase phase-transfer catalytic polymerization process of low molecular weight polystyrene - Google Patents
Two-phase phase-transfer catalytic polymerization process of low molecular weight polystyrene Download PDFInfo
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Abstract
The invention discloses a two-phase phase-transfer catalytic polymerization process of low molecular weight polystyrene. The two-phase phase-transfer catalytic polymerization process comprises the steps of: preparing raw materials; performing phase-transfer catalytic polymerization; separating; washing and the like. According to the process, a water-insoluble organic solvent and water are taken to be two-phase; a water-soluble initiator is adopted and is transferred to an organic phase under the action of a phase-transfer catalyst to initiate styrene polymerization; and the initiator and the phase-transfer catalyst in the polystyrene solution are removed through phase splitting and washing after the polymerization is finished to obtain pure polystyrene solution. The two-phase phase-transfer catalytic polymerization process has the advantages that: the polystyrene with low relative molecular weight and narrow molecular weight distribution can be prepared by using the process; the relative molecular mass of the polystyrene is 5,000-50,000; the prepared polystyrene basically contains no initiator; and thus, the alpha-site bromination in a bromination process is effectively avoided and the thermal stability of a product is obviously improved.
Description
Technical field
The present invention relates to a kind of polymerization technique of low-molecular-weight polystyrene, specifically a kind of two-phase phase-transfer catalysis polymerization technique of low-molecular-weight polystyrene belongs to flame retardant area.
Background technology
Brominated Polystyrene (being called for short BPS) is a kind of additive flame retardant of macromolecular material, has the bromine content height, good flame retardation effect, good heat resistance, little to the influence of resin impact resistance, no blooming, do not move, low toxicity, environmental protection, do not discharge carcinogenic advantages such as dioxin during burning, meeting European Union's " using some objectionable impurities instruction about restriction in electronic electric equipment " (" Restriction of the use of certain hazardous substance in electrical and electronic equipment " is called for short the RoHS instruction) and " about the waste electronic andelectrical equipment instruction " (" Waste Electrical and Electronic Equipment " is called for short the WEEE instruction) fully, is the best substitute products of Polybrominated biphenyl and Poly Brominated Diphenyl Ethers.(DE 2645711,1978-4-13 to be widely used for high melting temperature resins such as nylon, polyester, urethane, polystyrene fire-retardant; DE 2727483,1979-1-11; USP 4373049,1983-2-8).
BPS mainly contains two kinds of preparation methods at present: a kind of is that (EP 0277429,1988-10-8 for polystyrene phenyl ring bromo method; USP:4352909,1982-10-5); Another kind be the bromostyrene polymerization (USP:5369202,1994-11-29).
Polystyrene phenyl ring bromo method technology is simple, technical qualification are less demanding, invest lessly, cost is lower, and the bromine content of product can reach 68%, thereby flame retarding efficiency height, required fire retardant addition is less during use, and little to the physical and mechanical properties infringement of interpolation resin, cost performance is lower, and raw material polystyrene, bromine, bromine chloride are easy to get, and are suitable for producing in enormous quantities.Because the thermostability of Brominated Polystyrene is relevant with the content of alpha-alkyl bromine (or chlorine) in the Brominated Polystyrene, the thermostability of the more high Brominated Polystyrene of its content is more low.In polystyrene phenyl ring bromination, because Br or BrCl easily form bromine or chlorine radical, the hydrogen of α position on the substituted polystyrene main chain alkyl carbon, form alpha-alkyl bromine (or chlorine), alpha-alkyl bromine (or chlorine) content is higher in the obtained flame-retardant agent product, is 3000～6000mg/kg (in HBr) as the content of alkyl bromide among Pyrochek 68 PB.Because the existence of alpha-alkyl bromine (or chlorine) directly causes the Brominated Polystyrene thermal stability to descend, and occurs the decomposition of alpha-alkyl bromine (or chlorine) about 200 ℃.Alkyl bromide decomposed in materials processing temperature early stage or mid-term, discharged hydrogen bromide, had damaged the performance of material, caused the material variable color, etching apparatus, and influence the processing environment of material and the relevant personnel's health.
(USP 5369202,1994-11-29) for the bromostyrene polymerization.Do not contain a-alkyl bromide (or chlorine) on the Brominated Polystyrene main chain that this method is produced, so the thermal stability of this product, colourity are all fine, and high temperature is not easy to change.But this method exists following two shortcomings: 1. this technological operation operation is many, and the production cycle is long, and appointed condition requires high, and investment is big, the cost/performance ratio height of product; 2. the existence of bromine makes two keys be difficult to polymerization, so it is raw material production two bromo polystyrene that this method can only adopt dibromo-benzene ethene, can not adopt tribromo-benzene ethene is raw material production three bromo polystyrene, thereby limited the bromine content in the Brominated Polystyrene (having only about 60%), and unreacted monomer in the Brominated Polystyrene-difficulty volatilization solid bromostyrene is difficult to remove.Because bromine content is low, when using this product, the addition that reaches the same required fire retardant of flame retardant effect is relatively large, and this not only causes the rising of flame-retarded resin price, and has damaged the physical and mechanical properties of resin.
Owing to above reason, mainly be to adopt first method production Brominated Polystyrene at present both at home and abroad.Adopt this method to produce the Brominated Polystyrene of three trades mark, Pyrocheck 60 PB, Pyrocheck 68 PB and Pyrocheck LM as U.S. Ferro company.Domestic production producer all adopts this method basically.Bromo on the phenyl ring is electrophilic substitution, and Er α – alkyl bromide is on behalf of the free radical bromo.Therefore, in order to suppress α – alkyl bromide generation, the method that adopts is to add radical scavenger in the bromo process at present, but suppresses not thorough.Ideal measure is the existence of as far as possible avoiding producing in the polystyrene material of free radical, as the existence of various radical initiators.
The Brominated Polystyrene great majority of producing in the world at present and using are oligomers, as the molecular weight of Pyrocheck 60 PB, Pyrocheck 68 PB of Ferro company and Pyrocheck LM all below 200,000.This is that fusing point is higher because the Brominated Polystyrene molecular weight is bigger, and dispersiveness is poorer, and is poor with the consistency of resin, thereby influences processing and the mechanical property of resin.In addition, the relative molecular mass of Brominated Polystyrene distributes narrower.Otherwise, adds the big molecule of relative molecular mass in man-hour and also do not melt fully, and the little molecule of relative molecular mass has just begun decomposes.This shows that it is the key that improves the fire retardant quality that the relative molecular mass of control BPS and relative molecular mass distribute.For first method, the key that makes the BPS of the little and relative molecular mass narrowly distributing of relative molecular mass is that the relative molecular mass of used polystyrene is little, and relative molecular mass distributes narrow, and relative molecular mass should be less than 50,000, preferably less than 10,000.In addition, alpha-alkyl bromine (or chlorine) therefore, prevents that alpha-alkyl bromine (or chlorine) from distributing also very important for relative molecular mass and relative molecular mass to control BPS for causing the chain rupture of Brominated Polystyrene molecule.
Both at home and abroad about low-molecular-weight polystyrene preparation method's bibliographical information seldom.Only a small amount of bibliographical information can adopt Transfer Radical Polymerization (Liu Lin etc., coatings industry, 2007,37(11): 22-24; Xiao Chenglong etc., the Shandong Light Ind College journal, 2010,24(2): 25-28) and the free radical solution polymerization method (Dong Shuan etc., the functional polymer journal, 1997,10(1): 87-89).Problems such as the former exists temperature of reaction height, long reaction time, condition harshness, the styrene conversion rate is low, technology is immature also are difficult to realize industrial application at present.The latter not only can make the polystyrene of the little and relative molecular mass narrowly distributing of relative molecular mass by adopting processing parameters such as suitable solvent, initiator, and have technical maturity, simple, cost is low and be easy to advantage such as industrialization, but make the little polystyrene of relative molecular mass, initiator amount is generally bigger.Because used initiator is dissolved in organic solvent and boiling point than higher, therefore initiator content is higher in the prepared polystyrene, so that in bromo process subsequently, easily produce α – position bromo and the thermostability of product is reduced, as document (Dong Shuan etc., the functional polymer journal, 1997,10(1): the thermal weight loss during 250 ℃ of BPS that 87-89) according to said method makes surpasses 2%.
Summary of the invention
In order to solve the problem that above-mentioned free radical solution polymerization method exists, the present invention has designed a kind of two-phase phase-transfer catalysis polymerization technique of low-molecular-weight polystyrene, this technology is two-phase with water-fast organic solvent and water, adopt water soluble starter, this initiator is transferred to organic phase under the effect of phase-transfer catalyst, cause styrene polymerization, the intact back of polymerization is by phase-splitting and wash initiator and the phase-transfer catalyst of removing in the polystyrene solution, obtain purer polystyrene solution, by regulating processing parameters such as initiator type and consumption thereof, make relative molecular mass and be 5000～50000 polystyrene, cinnamic transformation efficiency is more than 96.0%.The low-molecular-weight polystyrene solution that obtains adds suitable solvent bromine chloride bromo again with the bromine chloride bromo or after removing solvent, the BPS bromine content that makes is up to more than 68%, and weightless 1% heat decomposition temperature surpasses 300 ℃, 155～168 ℃ of softening temperatures.
Technical scheme of the present invention is:
A kind of two-phase phase-transfer catalysis polymerization technique of low-molecular-weight polystyrene, the relative molecular mass of described polystyrene is 5000～50000, its processing step is as follows:
(1) raw material is prepared: weighing organic solvent, water, phase-transfer catalyst, initiator and vinylbenzene; Organic solvent, water and cinnamic mass ratio are 0.5～1.5 ︰, 0.5～1.5 ︰ 1; Phase-transfer catalyst and vinylbenzene mass ratio are 1 ︰ 30～80; Initiator and cinnamic mass ratio are 1 ︰ 3～7;
(2) phase-transfer catalysis polymerization: with organic solvent, water, phase-transfer catalyst, and the vinylbenzene of 30～36% initiator and 30～35% adds reactor, carry out polyreaction, when the material in the question response still is heated to polymerization temperature, drip remaining initiator and vinylbenzene, 1～6h drips off the back and continues reaction 1～6h, treats that styrene conversion stops heating after intact;
(3) separating, washing: above-mentioned reaction is cooled to room temperature with reaction mass after finishing, and leaves standstill phase-splitting, isolates water, and oil phase washes twice with water, obtains relative molecular mass and be 5000～50000 polystyrene solution;
Wherein, described initiator is water soluble starter or water soluble oxidized reduction initiating system; The polymerization temperature of described water soluble oxidized reduction initiating system is 25～75 ℃; The polymerization temperature of described water soluble starter is 75～98 ℃.
Described organic solvent is: hydrochloric ether, and as ethylene dichloride, methylene dichloride, trichloromethane or tetracol phenixin; Aromatic hydrocarbon or chlorination aromatic hydrocarbon are as benzene,toluene,xylene or chlorobenzene; Alkane is as normal hexane, octane or normal heptane.
Described water soluble starter is a kind of in ammonium persulphate, Sodium Persulfate, Potassium Persulphate or the azo diisobutyl amidine hydrochloride; Described water soluble oxidized reduction initiating is sodium bisulfite/ammonium persulphate, i.e. the mixture of sodium bisulfite and ammonium persulphate, mass ratio 1:0.8～1.2; Or ferrous sulfate/hydrogen peroxide, i.e. the mixture of ferrous sulfate and hydrogen peroxide, mass ratio 1:0.10～0.15.
Described phase-transfer catalyst is: quaternary ammonium salt, as Tetrabutyl amonium bromide, Trimethyllaurylammonium bromide or tri-n-octyl methyl ammonium chloride; Quaternary alkylphosphonium salt is as trioctylphosphine methyl phosphonium bromide or dodecyl trimethylammonium phosphonium bromide; Crown ether is as hexaoxacyclooctadecane-6-6, dibenzo-18-crown-6 (DB18C6) or dicyclohexyl-hexaoxacyclooctadecane-6-6; The open chain polyethers is as PEG400 or PEG600.
Preferred 40～55 ℃ of the polymerization temperature of described water soluble oxidized reduction initiating system; Preferred 80～90 ℃ of the polymerization temperature of described water soluble starter.
The dropping time of described residual styrene and initiator is preferably 3～5 h; Vinylbenzene drips the back and continues preferred 2～4 h of reaction times.
Preferred 0.9～1.1 ︰ 1 of described organic solvent and cinnamic mass ratio.
Preferred 1 ︰ 4～5 of described initiator and cinnamic mass ratio.
Preferred 1 ︰ 40～60 of described phase-transfer catalyst and cinnamic mass ratio.
Preferred 0.8～1.2 ︰ 1 of described water and cinnamic mass ratio.
The washing used water of oil phase and preferred 1.8～2.2 ︰ 1 of cinnamic mass ratio in the described separating, washing step.
The present invention substitutes traditional oil-soluble initiator by adopting water soluble starter, thereby is conducive to remove from product residual initiator and degradation production thereof.In addition, the present invention is by utilizing phase transfer catalysis, solved that water soluble starter is insoluble to oil phase and the problem that is difficult to cause styrene polymerization.
The invention has the advantages that: it is low to adopt technology of the present invention not only can make relative molecular weight, the polystyrene of narrow molecular weight distribution, the relative molecular mass of polystyrene is 5000～50000, and the polystyrene that makes does not contain initiator substantially, thereby effectively avoided bromo process Zhong α – position bromo and significantly improved the thermostability of product, the low-molecular-weight polystyrene solution that adopts technology of the present invention to obtain be among the BPS that makes of raw material bromine content up to more than 68%, weightless 1% heat decomposition temperature surpasses 300 ℃, 155～168 ℃ of softening temperatures.
Embodiment
Below the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein only is used for description and interpretation the present invention, and be not used in restriction the present invention.
Except as otherwise noted, the percentage ratio that adopts among the present invention is mass percent.
Embodiment 1
A kind of two-phase phase-transfer catalysis polymerization technique of low-molecular-weight polystyrene may further comprise the steps:
(1) raw material is prepared: weighing 200g vinylbenzene, 200.0g ethylene dichloride, 30.0g sodium bisulfite, 11.0g+200mL massfraction 10% ammonium persulphate (being that 11.0g ammonium persulphate and 200 mL massfractions are 10% ammonium persulfate solution), 5.0g Tetrabutyl amonium bromide and 150 mL deionized waters;
(2) 66.7g vinylbenzene, 200.0g ethylene dichloride, 30.0g sodium bisulfite, 11.0g ammonium persulphate, 5.0g Tetrabutyl amonium bromide and 150 mL deionized waters being joined 1L has in thermometer, condenser and the churned mechanically four-hole boiling flask, by the heating in water bath material, drip remaining 133.3g vinylbenzene and 200 mL10% ammonium persulfate solutions by dropping funnel respectively in 50 ℃～55 ℃, about 4h drips off, and continues insulation reaction 3h afterwards;
(3) be cooled to room temperature after reaction finishes, material be transferred to separating funnel leave standstill phase-splitting, the organic phase of telling is with twice of 200 mL * 2 deionized water wash.
Interpretation of result: the styrene conversion rate is the 99.7%(weighting method), the relative molecular mass Mn of gained polystyrene is 15400, molecular weight distribution is the Mw/Mn=1.45(GPC method).The BPS bromine content that the gained polystyrene solution makes through the direct bromo of bromide chloride is 68.5%, and weightless 1% heat decomposition temperature is 304 ℃, and softening temperature is 165 ℃.
Embodiment 2
A kind of two-phase phase-transfer catalysis polymerization technique of low-molecular-weight polystyrene may further comprise the steps:
(1) raw material is prepared: weighing 200g vinylbenzene, 200.0g ethylene dichloride, 30.0g sodium bisulfite, 11.0g+200 mL10% ammonium persulphate, 5.0g Tetrabutyl amonium bromide and 150 mL deionized waters;
(2) 66.7g vinylbenzene, 200.0g ethylene dichloride, 30.0g sodium bisulfite, 11.0g ammonium persulphate, 5.0g Tetrabutyl amonium bromide and 150 mL deionized waters being joined 1L has in thermometer, condenser and the churned mechanically four-hole boiling flask, by the heating in water bath material, drip remaining 133.3g vinylbenzene and 200 mL10% ammonium persulfate solutions by dropping funnel respectively in 40 ℃～45 ℃, about 4h drips off, and continues insulation reaction 3h afterwards;
(3) be cooled to room temperature after reaction finishes, material be transferred to separating funnel leave standstill phase-splitting, the organic phase of telling is with twice of 200 mL * 2 deionized water wash.
Interpretation of result: the styrene conversion rate is the 96.5%(weighting method), the relative molecular mass Mn of gained polystyrene is 27400, molecular weight distribution is the Mw/Mn=1.87(GPC method).The BPS bromine content that the gained polystyrene solution makes through the direct bromo of bromide chloride is 68.3%, and weightless 1% heat decomposition temperature is 293 ℃, and softening temperature is 145 ℃.
Embodiment 3
A kind of two-phase phase-transfer catalysis polymerization technique of low-molecular-weight polystyrene may further comprise the steps:
(1) raw material is prepared: weighing 200g vinylbenzene, 200.0g toluene, 30.0g sodium bisulfite, 11.0g+200 mL10% ammonium persulphate, 5.0g Tetrabutyl amonium bromide and 150 mL deionized waters;
(2) 66.7g vinylbenzene, 200.0g toluene, 30.0g sodium bisulfite, 11.0g ammonium persulphate, 5.0g Tetrabutyl amonium bromide and 150 mL deionized waters being joined 1L has in thermometer, condenser and the churned mechanically four-hole boiling flask, by the heating in water bath material, drip remaining 133.3g vinylbenzene and 200 mL10% ammonium persulfate solutions by dropping funnel respectively in 50 ℃～55 ℃, about 4h drips off, and continues insulation reaction 3h afterwards;
(3) be cooled to room temperature after reaction finishes, material be transferred to separating funnel leave standstill phase-splitting, the organic phase of telling is with twice of 200 mL * 2 deionized water wash.
Interpretation of result: the styrene conversion rate is the 99.5%(weighting method), the relative molecular mass Mn of gained polystyrene is 17400, molecular weight distribution is the Mw/Mn=1.55(GPC method).The BPS bromine content that the gained polystyrene solution makes through the direct bromo of bromide chloride is 68.5%, and weightless 1% heat decomposition temperature is 303 ℃, and softening temperature is 160 ℃.
Embodiment 4
A kind of two-phase phase-transfer catalysis polymerization technique of low-molecular-weight polystyrene may further comprise the steps:
(1) raw material is prepared: weighing 200g vinylbenzene, 200.0g ethylene dichloride, 14.0g+280 mL10% ammonium persulphate, 5.0g Tetrabutyl amonium bromide and 150 mL deionized waters;
(2) 66.7g vinylbenzene, 200.0g ethylene dichloride, 14.0g ammonium persulphate, 5.0g Tetrabutyl amonium bromide and 150 mL deionized waters being joined 1L has in thermometer, condenser and the churned mechanically four-hole boiling flask, by the heating in water bath material, drip remaining 133.3g vinylbenzene and 280 mL10% ammonium persulfate solutions with dropping funnel respectively in 78 ℃～82 ℃, about 4h drips off, and continues insulation reaction 3h afterwards;
(3) be cooled to room temperature after reaction finishes, material be transferred to separating funnel leave standstill phase-splitting, the organic phase of telling is with twice of 200 mL * 2 deionized water wash;
Interpretation of result: the styrene conversion rate is the 99.9%(weighting method), the relative molecular mass Mn of gained polystyrene is 6800, molecular weight distribution mw/mn=1.35.The BPS bromine content that the gained polystyrene solution makes through the direct bromo of bromide chloride is 68.9%,, weightless 1% heat decomposition temperature is 314 ℃, softening temperature is 159 ℃.
Embodiment 5
A kind of two-phase phase-transfer catalysis polymerization technique of low-molecular-weight polystyrene may further comprise the steps:
(1) raw material is prepared: weighing 200g vinylbenzene, 200.0g ethylene dichloride, 10.0g+200 mL10% ammonium persulphate, 5.0g Tetrabutyl amonium bromide and 150 mL deionized waters;
(2) 66.7g vinylbenzene, 200.0g ethylene dichloride, 10.0g ammonium persulphate, 5.0g Tetrabutyl amonium bromide and 150 mL deionized waters being joined 1L has in thermometer, condenser and the churned mechanically four-hole boiling flask, by the heating in water bath material, drip remaining 133.3g vinylbenzene and 200 mL10% ammonium persulfate solutions with dropping funnel respectively in 90 ℃～98 ℃, about 4h drips off, and continues insulation reaction 3h afterwards;
(3) be cooled to room temperature after reaction finishes, material be transferred to separating funnel leave standstill phase-splitting, the organic phase of telling is with twice of 200 mL * 2 deionized water wash.
Interpretation of result: the styrene conversion rate is the 99.9%(weighting method), the relative molecular mass Mn of gained polystyrene is 23600, molecular weight distribution mw/mn=2.13.The BPS bromine content that the gained polystyrene solution makes through the direct bromo of bromide chloride is 68.9%,, weightless 1% heat decomposition temperature is 301 ℃, softening temperature is 158 ℃.
Embodiment 6
A kind of two-phase phase-transfer catalysis polymerization technique of low-molecular-weight polystyrene may further comprise the steps:
(1) raw material is prepared: weighing 200g vinylbenzene, 200.0g ethylene dichloride, 10.0g+200 mL10% ammonium persulphate, 5.0g Tetrabutyl amonium bromide and 150 mL deionized waters;
(2) 66.7g vinylbenzene, 200.0g ethylene dichloride, 10.0g ammonium persulphate, 5.0g Tetrabutyl amonium bromide and 150 mL deionized waters being joined 1L has in thermometer, condenser and the churned mechanically four-hole boiling flask, by the heating in water bath material, drip remaining 133.3g vinylbenzene and 200 mL10% ammonium persulfate solutions with dropping funnel respectively in 78 ℃～82 ℃, about 4h drips off, and continues insulation reaction 3h afterwards;
(3) be cooled to room temperature after reaction finishes, material be transferred to separating funnel leave standstill phase-splitting, the organic phase of telling is with twice of 200 mL * 2 deionized water wash.
Interpretation of result: the styrene conversion rate is the 99.9%(weighting method), the relative molecular mass Mn of gained polystyrene is 26800, molecular weight distribution mw/mn=1.39.The BPS bromine content that the gained polystyrene solution makes through the direct bromo of bromide chloride is 68.9%,, weightless 1% heat decomposition temperature is 308 ℃, softening temperature is 168 ℃.
Embodiment 7
A kind of two-phase phase-transfer catalysis polymerization technique of low-molecular-weight polystyrene may further comprise the steps:
(1) raw material is prepared: weighing 200g vinylbenzene, 200.0g ethylene dichloride, 10.0g+200 mL10% ammonium persulphate, 5.0g Trimethyllaurylammonium bromide and 150 mL deionized waters;
(2) 66.7g vinylbenzene, 200.0g ethylene dichloride, 10.0g ammonium persulphate, 5.0g Trimethyllaurylammonium bromide and 150 mL deionized waters being joined 1L has in thermometer, condenser and the churned mechanically four-hole boiling flask, by the heating in water bath material, drip remaining 133.3g vinylbenzene and 200 mL10% ammonium persulfate solutions with dropping funnel respectively in 78 ℃～82 ℃, about 4h drips off, and continues insulation reaction 3h afterwards;
(3) be cooled to room temperature after reaction finishes, material be transferred to separating funnel leave standstill phase-splitting, the organic phase of telling is with twice of 200 mL * 2 deionized water wash.
Interpretation of result: the styrene conversion rate is the 99.8%(weighting method), the relative molecular mass Mn of gained polystyrene is 29800, molecular weight distribution mw/mn=1.59.The BPS bromine content that the gained polystyrene solution makes through the direct bromo of bromide chloride is 68.7%,, weightless 1% heat decomposition temperature is 305 ℃, softening temperature is 162 ℃.
Embodiment 8
A kind of two-phase phase-transfer catalysis polymerization technique of low-molecular-weight polystyrene may further comprise the steps:
(1) raw material is prepared: weighing 200g vinylbenzene, 100.0g normal heptane, 10.0g+200 mL10% ammonium persulphate, 2.5g PEG400 and 100 mL deionized waters;
(2) 60.0g vinylbenzene, 100.0g normal hexane, 10.0g ammonium persulphate, 2.5g PEG400 and 100 mL deionized waters being joined 1L has in thermometer, condenser and the churned mechanically four-hole boiling flask, by the heating in water bath material, drip remaining 140.0g vinylbenzene and 200 mL10% ammonium persulfate solutions with dropping funnel respectively in 82 ℃～90 ℃, about 3h drips off, and continues insulation reaction 4h afterwards;
(3) be cooled to room temperature after reaction finishes, material be transferred to separating funnel leave standstill phase-splitting, the organic phase of telling is with twice of 180 mL * 2 deionized water wash.
Interpretation of result: the styrene conversion rate is the 98.3%(weighting method), the relative molecular mass Mn of gained polystyrene is 23800, molecular weight distribution mw/mn=1.79.The BPS bromine content that the gained polystyrene solution makes through the direct bromo of bromide chloride is 68.1%,, weightless 1% heat decomposition temperature is 302 ℃, softening temperature is 156 ℃.
Embodiment 9
A kind of two-phase phase-transfer catalysis polymerization technique of low-molecular-weight polystyrene may further comprise the steps:
(1) raw material is prepared: weighing 200g vinylbenzene, 200.0g chlorobenzene, 30.0g sodium bisulfite, 11.0g+200mL massfraction 10% ammonium persulphate, 3.3g trioctylphosphine methyl phosphonium bromide and 300 mL deionized waters;
(2) 70.0g vinylbenzene, 200.0g chlorobenzene, 30.0g sodium bisulfite, 11.0g ammonium persulphate, 3.3g trioctylphosphine methyl phosphonium bromide and 300 mL deionized waters being joined 1L has in thermometer, condenser and the churned mechanically four-hole boiling flask, by the heating in water bath material, in 25 ℃～40 ℃ ammonium persulfate solutions that drip remaining 130.0g vinylbenzene and 200mL massfraction 10% respectively with dropping funnel, about 5h drips off, and continues insulation reaction 2h afterwards;
(3) be cooled to room temperature after reaction finishes, material be transferred to separating funnel leave standstill phase-splitting, the organic phase of telling is with twice of 220 mL * 2 deionized water wash.
Interpretation of result: the styrene conversion rate is the 99.6%(weighting method), the relative molecular mass Mn of gained polystyrene is 28800, molecular weight distribution mw/mn=1.56.The BPS bromine content that the gained polystyrene solution makes through the direct bromo of bromide chloride is 68.9%,, weightless 1% heat decomposition temperature is 307 ℃, softening temperature is 164 ℃.
Embodiment 10
A kind of two-phase phase-transfer catalysis polymerization technique of low-molecular-weight polystyrene may further comprise the steps:
(1) raw material is prepared: weighing 200g vinylbenzene, 300.0g tetracol phenixin, 30.0g sodium bisulfite, 11.0g+200mL massfraction 10% ammonium persulphate, 6.7g dibenzo-18-crown-6 (DB18C6) and 200 mL deionized waters;
(2) 65.0g vinylbenzene, 300.0g tetracol phenixin, 30.0g sodium bisulfite, 11.0g ammonium persulphate, 6.7g dibenzo-18-crown-6 (DB18C6) and 200 mL deionized waters being joined 1L has in thermometer, condenser and the churned mechanically four-hole boiling flask, by the heating in water bath material, in 55 ℃～75 ℃ ammonium persulfate solutions that drip remaining 135.0g vinylbenzene and 200mL massfraction 10% respectively with dropping funnel, about 1h drips off, and continues insulation reaction 6h afterwards;
(3) be cooled to room temperature after reaction finishes, material be transferred to separating funnel leave standstill phase-splitting, the organic phase of telling is with twice of 220 mL * 2 deionized water wash.
Interpretation of result: the styrene conversion rate is the 98.5%(weighting method), the relative molecular mass Mn of gained polystyrene is 35600, molecular weight distribution mw/mn=1.89.The BPS bromine content that the gained polystyrene solution makes through the direct bromo of bromide chloride is 68.2%,, weightless 1% heat decomposition temperature is 304 ℃, softening temperature is 155 ℃.
It should be noted that at last: the above only is the preferred embodiments of the present invention, be not limited to the present invention, although with reference to previous embodiment the present invention is had been described in detail, for a person skilled in the art, it still can be made amendment to the technical scheme that aforementioned each embodiment puts down in writing, and perhaps part technical characterictic wherein is equal to replacement.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (6)
1. the two-phase phase-transfer catalysis polymerization process of a low-molecular-weight polystyrene is characterized in that step is as follows:
(1) raw material is prepared: weighing organic solvent, water, phase-transfer catalyst, initiator and vinylbenzene; Organic solvent, water and cinnamic mass ratio are 0.5～1.5 ︰, 0.5～1.5 ︰ 1; Phase-transfer catalyst and cinnamic mass ratio are 1 ︰ 30～80; Initiator and cinnamic mass ratio are 1 ︰ 3～7;
(2) phase-transfer catalysis polymerization: with organic solvent, water, phase-transfer catalyst, and the vinylbenzene of 30～36% initiator and 30～35% adds reactor, carry out polyreaction, when the material in the question response still is heated to polymerization temperature, drip remaining initiator and vinylbenzene, 1～6h drips off the back and continues reaction 1～6h, treats that styrene conversion stops heating after intact;
(3) separating, washing: above-mentioned reaction is cooled to room temperature with reaction mass after finishing, and leaves standstill phase-splitting, isolates water, and oil phase washes twice with water, obtains number-average molecular weight and be 5000～50000 polystyrene solution;
Wherein, described initiator is water soluble starter or water soluble oxidized reduction initiating system; The polymerization temperature of described water soluble oxidized reduction initiating system is 25～75 ℃; The polymerization temperature of described water soluble starter is 75～98 ℃;
Described water soluble starter is a kind of in ammonium persulphate, Sodium Persulfate, Potassium Persulphate or the azo diisobutyl amidine hydrochloride;
Described water soluble oxidized reduction initiating is that sodium bisulfite and ammonium persulphate are by the mixture of mass ratio 1:0.8～1.2.
2. according to the two-phase phase-transfer catalysis polymerization process of the described low-molecular-weight polystyrene of claim 1, it is characterized in that: described phase-transfer catalyst is: a kind of in quaternary ammonium salt, quaternary alkylphosphonium salt, crown ether or the open chain polyethers.
3. according to the two-phase phase-transfer catalysis polymerization process of claim 1 or 2 described low-molecular-weight polystyrenes, it is characterized in that: the polymerization temperature of described water soluble oxidized reduction initiating system is 40～55 ℃; The polymerization temperature of described water soluble starter is 80～90 ℃.
4. according to the two-phase phase-transfer catalysis polymerization process of claim 1 or 2 described low-molecular-weight polystyrenes, it is characterized in that: the dropping time of described residual styrene and initiator is 3～5 h; It is 2～4 h that vinylbenzene drips the back continuation reaction times.
5. according to the two-phase phase-transfer catalysis polymerization process of claim 1 or 2 described low-molecular-weight polystyrenes, it is characterized in that: described organic solvent and cinnamic mass ratio are 0.9～1.1 ︰ 1; Described initiator and cinnamic mass ratio are 1 ︰ 4～5; Described phase-transfer catalyst and cinnamic mass ratio are 1 ︰ 40～60; Described water and cinnamic mass ratio are 0.8～1.2 ︰ 1.
6. according to the two-phase phase-transfer catalysis polymerization process of claim 1 or 2 described low-molecular-weight polystyrenes, it is characterized in that: the washing used water of oil phase and cinnamic mass ratio are 1.8～2.2 ︰ 1 in the described step (3).
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