CN104177516A - Bromized aliphatic olefin/vinyl aromatic copolymer flame retardant and preparation method thereof - Google Patents
Bromized aliphatic olefin/vinyl aromatic copolymer flame retardant and preparation method thereof Download PDFInfo
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Abstract
The invention provides a bromized aliphatic olefin/vinyl aromatic copolymer flame retardant which serves as a common flame retardant which substitutes HBCD and is used in the plastic industry. The bromized aliphatic olefin component of the bromized aliphatic olefin/vinyl aromatic copolymer flame retardant at least contains a bromized olefin monomer; the bromized vinyl aromatic component comprises 2-bromostyryl, 4-bromostyryl, 2,4-dibromostyryl, 6-bromostyryl and 2,4,6-tribromostyryl. Meanwhile, the invention further relates to a preparation method of the bromized aliphatic olefin/vinyl aromatic copolymer flame retardant.
Description
Technical field
The present invention relates to chemical industry plastics additive field, relate in particular to a kind of thermal stable bromated aliphatics alkene/vinyl aromatic copolymer fire retardant, and the preparation method of this type of bromination aliphatics alkene/vinyl aromatic copolymer.
Background technology
Hexabromocyclododecane (HBCD) is that a kind of general fire retardant (FR) has a wide range of applications in flame retardant area.But research finds, HBCD has biological accumulation in one or more bodies, to the toxicity of waterplant and to there being lasting environmental influence.This is with regard to needing certain laws and rules to limit and control for the use of HBCD, to reduce it for the impact of environmental and biological materials.Meanwhile, find a kind of in vivo without accumulation, the fire retardant of the low impact of environment is just seemed to extremely important.
Due to organism for polymkeric substance without absorbing the low migration of polymkeric substance in material simultaneously, aggretion type brominated flame-retardant is exactly a selection that replaces HCBD.What is more important, aggretion type brominated flame-retardant itself just can adapt to by adjusting segment distribution, molecular weight distribution, the bromination rate of material the processing request of different polymeric materials.
The working method that polymkeric substance is conventional has injection moulding, extrudes, miscible and foaming polymerization.For these different working methods, for the requirement of fire retardant, be different.Wherein former three needs main thermostability the latter who focuses on material may more focus on the consistency of material.Take polystyrene as example, because polystyrene is in extruding injection moulding, melt-mixing and extrusion and foaming process, its processing temperature is sometimes over 200 ℃, even reach 230 ℃, require its flame-retardant additive also should possess good thermostability, to prevent that it from producing thermal destruction in the polystyrene course of processing.If flame-retardant additive decomposes during expressing technique or foam process, be faced with following several problem: fire retardant loss; The reduction of fire retardant performance; The generation of corrodibility degradation production, and these degradation productions exist environment and the potential harm of human body.Therefore flame-retardant additive is to focus on its thermostability at expressing technique or foam process temperature, and these processing temperatures generally surpass 200 ℃, even reach 230 ℃.But for the bromide fire retardant of polystyrene foamed, except above-mentioned thermostability, for them, also more focus on its consistency in material.The special emphasis that requires for material is placed on itself and foaming post polymerization thing, monomer before foaming, and the consistency of pore forming material.On this basis, improve as far as possible the flame retardant properties of fire retardant.For the bromide fire retardant of polystyrene foamed, it is generally acknowledged that its bromine content is higher, flame retardant properties is better.Its flame retardant properties can be measured by limiting oxygen index(LOI) (LOI), and its value is higher, illustrates that flame retardant properties is better.For example, after HBCD is added in Expandable Polystyrene (EPS), bromine content LOI value of its foam materials of preparing 0.6% time is greater than 25.
Many open source literatures have been reported the synthetic of brominated polybutadiene homopolymer, but owing to there is no enough thermostabilitys, it can not be used as the substitute of HBCD.Comprising:
French Patent FR 1506872 has described the synthetic of polyhutadiene bromination homopolymer, wherein polyhutadiene preferred polymers be 5 to 200, most preferably 10 to 50 and its 1,2-group percentage is greater than 50%.Take tetracol phenixin and butanols as mixed solvent, adopt bromine to carry out bromination.
CN102174149 discloses the method for preparing butadiene bromide copolymer.But the specific features of butadienecopolymer before its undeclared bromination.
WO2008/021417 has described the method for brominated butadiene polymers.Bromizating agent is phenyl trialkyl tribromide ammonium, benzyl trialkyl tribromide ammonium or tetraalkyl tribromide ammonium.The method is carried out in solution with starting polymer.The highly selective bromination that realizes aliphatic carbon-carbon double bond, aromatic ring is substantially unaffected.
CN102939308 discloses the method for brominated butadiene polymers.Bromizating agent is tetraethyl-list brometo de amonio.The method is carried out in solution with starting polymer.
In order to improve the thermostability of fire retardant, improve it at the application performance of materials processing, people are incorporated into aromatic nucleus in polyhutadiene main chain.
JP 571113372 discloses a kind of material of Expandable Polystyrene (EPS) of the fire retardant (SBR) of preparing containing bromination irregular phenylethylene-butadiene copolymer rubber.This SBR material is liquid, has lower molecular weight, and application performance is restricted.
CN 101305022 discloses the method for preparing brominated butadiene/vinyl aromatic copolymer.Wherein preferred molecular weight is in 50,000 to 100,000 scope, and the mixture of tetrahydrofuran (THF) or tetracol phenixin and alcohol of take is solvent, and adopting bromine or bromination is that aliphatic double bonds in bromizating agent brominated polymer is prepared brominated polymer.Its 5% thermal weight loss temperature is more than 200 ℃.Bromination prepolymer medium vinyl aromatic monomer content is greater than 5%.But it does not carry out bromination by aromatic nucleus.
Above two pieces of documents, have realized the highly selective bromination of fatty carbon-carbon double bond, and aromatic ring is substantially unaffected.But occurred a new problem, that is exactly the introducing due to aromatic nucleus simultaneously, the bromine content of polymkeric substance is reduced, the flame retardant properties of fire retardant declines.
Summary of the invention
Technical problem to be solved by this invention provides a kind of bromination aliphatics alkene/vinyl aromatic copolymer fire retardant, as replacing HBCD for the general fire retardant of plastic industry.The preparation method who simultaneously also relates to this kind of bromination aliphatics alkene/vinyl aromatic copolymer fire retardant.
The bromination fat alkene composition of this bromination aliphatics alkene/vinyl aromatic copolymer fire retardant, at least comprise a kind of brominated olefins monomer, ethylene bromide base aromatic component comprises 2-bromstyrol base, 4-bromstyrol base, 2,4-Dowspray 9 base, 6-bromstyrol base, 2,4,6-phenylstilbene bromide base.
Further, described bromination aliphatics alkene/vinyl aromatic copolymer fire retardant, it is characterized in that: the fatty alkene composition of described aliphatics alkene/vinyl aromatic copolymer, at least comprise a kind of diene monomers or monoolefine monomer, diene monomers comprises divinyl, isoprene, and monoolefine monomer comprises methacrylic acid, acrylate.
Further, described bromination aliphatics alkene/vinyl aromatic copolymer fire retardant, it is characterized in that: the aromatic component of described aliphatics alkene/vinyl aromatic copolymer, at least one is selected from vinylbenzene, and this multipolymer can be segmented copolymer, random copolymers or graft copolymer.
Further, described bromination aliphatics alkene/vinyl aromatic copolymer fire retardant, it is characterized in that: the weight-average molecular weight of described aliphatics alkene/vinyl aromatic copolymer is between 1000 to 60000, and preferable weight-average molecular weight is between 5000-10000.
A kind of method of preparing bromination aliphatics alkene/vinyl aromatic copolymer involved in the present invention, described method comprises:
Step 1) adds fatty alcohol to mix after aliphatics alkene/vinyl aromatic copolymer is uniformly dissolved with stirring solvent, in this solution, drip bromizating agent, and make mixture reaction until the aliphatics diene units of required ratio by bromination, bromination reaction is measured the aliphatic double bonds content of bromination in the multipolymer after bromination by 1H-NMR;
Step 2) add subsequently lewis acid catalyst to continue reaction for some time, until the aromatic nucleus unit of required ratio is by bromination in aliphatics alkene/vinyl aromatic copolymer, bromination reaction is measured bromine content on the aromatic nucleus of bromination in the multipolymer after bromination by 1H-NMR;
Step 3) obtains after the polymkeric substance of required bromine content in reaction, by washing, precipitation or filtered and recycled program, from reaction soln, remove by product, then filtrate is removed to residual by product by silica gel or ion exchange resin bed, polymkeric substance is deposited in and in methyl alcohol, reclaims brominated polymer.
Aliphatics alkene/vinyl aromatic copolymer in described step 1), wherein comprise vinyl aromatic composition weight percent and be 5 to 90% and aliphatics alkene composition weight percent be 10 to 95%, at least 800 weight-average molecular weight;
Further, the fatty alkene composition of described aliphatics alkene/vinyl aromatic copolymer, at least comprise a kind of diene monomers or monoolefine monomer, diene monomers comprises divinyl, isoprene, monoolefine monomer comprises methacrylic acid, acrylate, and aliphatics alkene/vinyl aromatic copolymer can be segmented copolymer, random copolymers or graft copolymer.
In described step 1), bromizating agent is the mixture that bromizating agent comprises bromine and free radical scavenger.
Further, substantially do not having under free radical substitution reaction, bromination ion is with cation state and aliphatic chain alkene generation bromination reaction, preferably under free radical substitution reaction, carries out not having completely; In fatty alkene bromination process, add free radical scavenger or adopt the method for preferred bromizating agent or solvent to prepare brominated polymer, it has enough low tertiary bromine content, can avoid the unsettled polymkeric substance of Heat of Formation, indirect indexes using 5% thermal weight loss temperature as tertiary bromine content, 5% thermal weight loss temperature shows while being greater than 200 ℃, there is enough low tertiary bromine content, preferably 5% thermal weight loss temperature be greater than 205 ℃, more preferably greater than 210 ℃, even more preferably greater than 220 ℃.
Further, described bromizating agent comprises bromine and tribromide, and tribromide comprises tribromide pyridine, tribromide phenyltrimethyammonium, tribromide tetra-allkylammonium.
Solvent in described step 1), under atmospheric pressure, solvent has the boiling point lower than 100 ℃ (particularly lower than 80 ℃), and unmixing substantially in water, is sprotic, and not containing being attached to hydrogen atom or the oxygen on tertiary carbon atom; Solvent ratio water more easily volatilizees, and easily from water, removes.Can select ethers as tetrahydrofuran (THF); Halogenated alkane is as tetracol phenixin, chloroform, methylene dichloride, bromochloromethane and 1,2-ethylene dichloride; Hydro carbons is as hexanaphthene, pentamethylene, and cyclooctane and toluene, and halogenated aromatic compound is as bromobenzene, chlorobenzene and dichlorobenzene;
Further, halogenated alkane, containing the naphthenic hydrocarbon and the halogenated aromatic compound that are attached to the hydrogen atom on tertiary carbon atom, be not preferred solvent.Two kinds of especially preferred solvents are ethylene dichloride and hexanaphthene.
In described step 1), select the amount of fatty alcohol, making, with respect to every mole of elemental bromine in bromizating agent, provides at least 0.5 mole of fatty alcohol, and starting fat family alkene/vinyl aromatic copolymer remains dissolved in reaction mixture.Some fatty alcohols play contrary solvent (antisolvents) effect for initial multipolymer, so their excessive existence may make initial multipolymer precipitate from solution.The amount of fatty alcohol is 0.5-6 moles/mole elemental bromine, and preferred amount is 0.75-3.5 moles/mole elemental bromine, and best preferred amount is 1.00-1.05 moles/mole elemental bromine.Can use the amount over this tittle, prerequisite is that initial multipolymer keeps solubilized.Conventionally, seldom need to use over 1 moles of alcohol per mole elemental bromine.
Described step 2) Lewis acid in comprises metallic antimony, titanium, iron or tin and halogenide thereof.
Recycling step in described step 3), also can be used aqueous solution of sodium bisulfite fully to wash from the filtrate of ion exchange resin bed outflow and may have the unreacted bromizating agent filtrate with neutralization or cancellation.
Described in described step 3), the blend of brominated copolymer comprises flame-retardant additive, flame retardant adjuvants, thermo-stabilizer, UV light stabilizing agent, nucleator, antioxidant, whipping agent, acid scavenger and tinting material.
From the invention described above content, compared to the prior art, tool of the present invention has the following advantages:
The present invention carries out bromination reaction to aliphatic double bonds and aromatic nucleus respectively, on the basis of aliphatic chain high selectivity bromination, further bromination aromatic nucleus, the bromination rate of raising polymkeric substance, and then the flame retardant properties of raising material, there is extraordinary thermostability and flame retardant properties.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Embodiment 1
To in 6.6g (polystyrene-b-divinyl) multipolymer (the polyhutadiene unit of 0.075 mole of polymerized) and 70 ml carbon tetrachloride solutions, join in the 250ml there-necked flask that is equipped with mechanical stirrer and constant pressure funnel, after stirring and dissolving is even, add the n-butanols of 25ml to mix.At room temperature, to the bromine that drips 12.6 g (0.08 mole) in solution, in 20 min, dropwise.Reaction mixture is shown as heat release in bromine adding procedure, and the top temperature of reaction process is 45 ℃.To under reaction mixture room temperature, continue reaction after 15 hours, 0.01g adds iron trichloride, continues reaction 2h, then adds the 20wt% aqueous solution of sodium bisulfite of 50 ml.Then continue to stir 15 minutes, add afterwards the methylene dichloride of 60ml.Reaction mixture is transferred to separating funnel, and upper strata is water, and lower floor is organic phase.
Organic phase is washed with 50ml distilled water, subsequently with the washing of 50ml saturated nacl aqueous solution.Organic phase after washing joins in the methyl alcohol of 5 times excessive (based on liquor capacities), and brominated polymer is precipitated from the organic phase washing.By the polymer filtration of precipitation and at 80 ℃, vacuum-drying, spend the night, obtain the brominated polymer of 16.9g (88% isolated yield).The 1H-NMR of brominated polymer shows 2.3% unreacted pair of key, and 4.5% fragrant ring hydrogen is replaced by bromine, and TGA analyzes 5% weightless temperature that shows 225 ℃.
Embodiment 2
In will 6.6g poly-(vinylbenzene-b-divinyl) multipolymer (the polyhutadiene unit of 0.075 mole of polymerized) and 70 ml dichloromethane solutions, join in the 250ml there-necked flask that is equipped with mechanical stirrer and constant pressure funnel, after stirring and dissolving is even, add the n-butanols of 25ml to mix.After polymer dissolution, solution is cooled in ice bath to 1 ℃, to the bromine that drips 12.6 g (0.008 mole) in solution, in 20 min, dropwise, keep in reaction flask temperature in or lower than 7 ℃, continue to stir after 20 minutes, add 0.01g to add iron trichloride, continue reaction 30min, remove ice bath, and by 20% aqueous solution of sodium bisulfite (51g) for reaction soln solution, follow water (50g), then use saturated sodium-chloride water solution (59g) washing, the rear dichloromethane extraction of using.Organic phase after washing joins in the methyl alcohol of 5 times excessive (based on liquor capacities), brominated polymer is precipitated from the organic phase washing, by the polymer filtration of precipitation and at 80 ℃, vacuum-drying, spend the night, obtain the brominated polymer of 16.5g (86% isolated yield).The 1H-NMR of brominated polymer shows 1.8% unreacted pair of key, and 4.5 % virtue ring hydrogens are replaced by bromine, and TGA analyzes 5% weightless temperature that shows 223 ℃.
Embodiment 3
In will 6.6g poly-(vinylbenzene-b-divinyl) multipolymer (the polyhutadiene unit of 0.075 mole of polymerized) and 70 ml dichloromethane solutions, join in the 250ml there-necked flask that is equipped with mechanical stirrer and constant pressure funnel, after stirring and dissolving is even, add the n-butanols of 25ml to mix.After polymer dissolution, solution is cooled in ice bath to 1 ℃.In solution, drip 20 ml containing the THF solution of 25.6 g tribromide pyridines (0.008 mole), in 30 min, dropwise.Keep in reaction flask temperature in or lower than 7 ℃, continue to stir after 20 minutes, add 0.01g to add iron trichloride, continue reaction 30min, remove ice bath; And reaction soln is removed to by product hydrogen pyridinium bromide (PHB) by filtration, by resulting polymers solution by cation exchange resin bed to remove residual PHB from solution, then use 20% aqueous solution of sodium bisulfite (51g), follow water (50g), then use saturated sodium-chloride water solution (59g) washing, the rear dichloromethane extraction of using.Organic phase after washing joins in the methyl alcohol of 5 times excessive (based on liquor capacities), brominated polymer is precipitated from the organic phase washing, by the polymer filtration of precipitation and at 80 ℃, vacuum-drying is spent the night, obtain the brominated polymer of 16.5g (86% isolated yield), the 1H-NMR of brominated polymer shows 1.3% unreacted pair of key, 4.8 % virtue ring hydrogens are replaced by bromine, and TGA analyzes 5% weightless temperature that shows 228 ℃, by filtration, remove by product hydrogen pyridinium bromide (PHB), by resulting polymers solution by cation exchange resin bed to remove residual PHB from solution.
Thermal performance analysis and flame retardant properties analysis
Thermal weight loss temperature test
Under the heating rate of TGA 400 10 ℃/min in the scope of 50 to 600 ℃ that use Perkinelmer company produces, under nitrogen atmosphere, (flow velocity is 20mL/min) tests (sample quality is 8-12 mg).The method provides 5% thermal weight loss temperature of sample, and initial weightless temperature.
Molecular weight test
Molecular weight test is carried out on HP 1090 HPLC type gel permeation chromatographs, separator column model 5 mm Phenogel columns (linear 300*4.6 mm, 5 micro), 36 ℃ of column temperatures, moving phase is tetrahydrofuran (THF), and divinyl is standard substance, differential detector.
Nucleus n-ness spectrum test
Nucleus magnetic resonance test is carried out on Varian Unity Inova 400, and the deuterium band chloroform of take is solvent, and TMS is interior mark, and probe temperature is 25 ℃.
Oxygen index test
According to GB/T 2406.2, carry out LOI test.For solid sample, the sample of preparation 100mm * 6.5mm * 1.5mm.For foam sample, improve and relate to the foam rods of using the production of foam yarn mould to there is 5mm girth and rod is cut into the test of 150mm progress row.
According to embodiment 3, be prepared as follows respectively bromo polyhutadiene styrene polymer.And according to thermostability and the flame retardant properties of the test procedure mensuration material of standard, its measurement result and flame retardant properties are as follows:
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. bromination aliphatics alkene/vinyl aromatic copolymer fire retardant, it is characterized in that bromination fat alkene composition, at least comprise a kind of brominated olefins monomer, ethylene bromide base aromatic component comprises 2-bromstyrol base, 4-bromstyrol base, 2,4-Dowspray 9 base, 6-bromstyrol base, 2,4,6-phenylstilbene bromide base.
2. a kind of bromination aliphatics alkene/vinyl aromatic copolymer fire retardant according to claim 1, it is characterized in that: the fatty alkene composition of described aliphatics alkene/vinyl aromatic copolymer, at least comprise a kind of diene monomers or monoolefine monomer, diene monomers comprises divinyl, isoprene, and monoolefine monomer comprises methacrylic acid, acrylate.
3. a kind of bromination aliphatics alkene/vinyl aromatic copolymer fire retardant according to claim 1, it is characterized in that: the aromatic component of described aliphatics alkene/vinyl aromatic copolymer, at least one is selected from vinylbenzene, and this multipolymer can be segmented copolymer, random copolymers or graft copolymer.
4. a kind of bromination aliphatics alkene/vinyl aromatic copolymer fire retardant according to claim 1, it is characterized in that: the weight-average molecular weight of described aliphatics alkene/vinyl aromatic copolymer is between 1000 to 60000, and preferable weight-average molecular weight is between 5000-10000.
5. a method of preparing bromination aliphatics alkene/vinyl aromatic copolymer, described method comprises:
Step 1) adds fatty alcohol to mix after aliphatics alkene/vinyl aromatic copolymer is uniformly dissolved with stirring solvent, in this solution, drip bromizating agent, and make mixture reaction until the aliphatics diene units of required ratio by bromination, bromination reaction is measured the aliphatic double bonds content of bromination in the multipolymer after bromination by 1H-NMR;
Step 2) add subsequently lewis acid catalyst to continue reaction for some time, until the aromatic nucleus unit of required ratio is by bromination in aliphatics alkene/vinyl aromatic copolymer, bromination reaction is measured bromine content on the aromatic nucleus of bromination in the multipolymer after bromination by 1H-NMR;
Step 3) obtains after the polymkeric substance of required bromine content in reaction, by washing, precipitation or filtered and recycled program, from reaction soln, remove by product, then filtrate is removed to residual by product by silica gel or ion exchange resin bed, polymkeric substance is deposited in and in methyl alcohol, reclaims brominated polymer.
6. a kind of method of preparing bromination aliphatics alkene/vinyl aromatic copolymer according to claim 5, it is characterized in that: in described step 1), solvent can select ethers as tetrahydrofuran (THF), or halogenated alkane is as tetracol phenixin, chloroform, methylene dichloride, bromochloromethane and 1,2-ethylene dichloride, or hydro carbons is if hexanaphthene, pentamethylene, cyclooctane and toluene and halogenated aromatic compound are as bromobenzene, chlorobenzene and dichlorobenzene.
7. a kind of method of preparing bromination aliphatics alkene/vinyl aromatic copolymer according to claim 5, it is characterized in that: described bromizating agent comprises bromine and tribromide, tribromide comprises tribromide pyridine, tribromide phenyltrimethyammonium, tribromide tetra-allkylammonium.
8. a kind of method of preparing bromination aliphatics alkene/vinyl aromatic copolymer according to claim 5, it is characterized in that: described step 2), the catalyzer of the bromination reaction of aromatic nucleus is Lewis acid, and Lewis acid comprises metallic antimony, titanium, iron or tin and halogenide thereof.
9. a kind of method of preparing bromination aliphatics alkene/vinyl aromatic copolymer according to claim 5, is characterized in that: the filtrate that also can use aqueous solution of sodium bisulfite fully to wash in described step 3) to flow out from ion exchange resin bed is with neutralization or the unreacted bromizating agent of cancellation filtrate.
10. a kind of method of preparing bromination aliphatics alkene/vinyl aromatic copolymer according to claim 5, is characterized in that: the blend of described brominated copolymer comprises flame-retardant additive, flame retardant adjuvants, thermo-stabilizer, UV light stabilizing agent, nucleator, antioxidant, whipping agent, acid scavenger and tinting material.
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| CN115141297A (en) * | 2022-07-07 | 2022-10-04 | 李旭东 | Degradable polystyrene synthesis method based on nitrobenzyl disulfide and pyridinium ester block macromolecular azo initiator |
| CN115141297B (en) * | 2022-07-07 | 2024-02-20 | 广东蓝海包装新技术有限公司 | Degradable polystyrene synthesis method based on nitrobenzyl disulfide and pyridinium ester block macromolecular azo initiator |
| CN115010857A (en) * | 2022-07-25 | 2022-09-06 | 北京工商大学 | Preparation method of high-thermal-stability brominated butadiene-styrene copolymer |
| CN115010857B (en) * | 2022-07-25 | 2023-09-29 | 北京工商大学 | Preparation method of brominated butadiene-styrene copolymer with high thermal stability |
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