CN104592466A - Halogenated polymer and preparation method thereof - Google Patents
Halogenated polymer and preparation method thereof Download PDFInfo
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- CN104592466A CN104592466A CN201310522168.4A CN201310522168A CN104592466A CN 104592466 A CN104592466 A CN 104592466A CN 201310522168 A CN201310522168 A CN 201310522168A CN 104592466 A CN104592466 A CN 104592466A
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Abstract
The invention relates to a halogenated polymer. The polymer has a structure of S1-I/B-S2 before halogenation, wherein S1 and S2 are polystyrene block, I/B represents a random compolymerization segment. In the halogenated block copolymer, 0.4-80% of carbon-carbon double bonds in an isoprene monomer unit are halogenated, and the ratio of the halogenation degree of carbon-carbon double bonds in a butadiene monomer unit to the halogenation degree of carbon-carbon double bonds in the isoprene monomer unit does not exceed 0.01. The invention also relates to a method for preparing the halogenated multiblock copolymer. The halogenated multiblock copolymer is capable of effectively improving the compatibility, also rising of the glass transition temperature is not too obvious, and thus the bonding performance is influenced when the halogenated multiblock copolymer is applied to a pressure-sensitive adhesive, and especially the peeling strength of the pressure-sensitive adhesive is influenced.
Description
Technical field
The present invention relates to a kind of halogenation triblock copolymer.More specifically, the present invention relates to the halogenide of the triblock copolymer of a kind of vinylbenzene, divinyl and isoprene.The invention still further relates to the method preparing described halogenation triblock copolymer in addition.
Background technology
Conjugated diene-styrene block copolymer generally includes SBS, SIS etc., and this base polymer is often for tackiness agent, plastic modifier, asphalt modifier etc.Due in the application, easily be cross-linked when SBS is heated and melt viscosity is increased, SIS is then easy to go bad because of degraded, therefore in recent years have developed the ternary block polymer of a kind of vinylbenzene, divinyl and isoprene to overcome these two kinds of polymkeric substance produced problem in the application.But because this kind of polymer polarity is lower, often need when these applications through polar-modified, to improve their bond properties or compatibility performance.Method of modifying comprises terminal groups modification, and common way adds polarity modifier after completion of polymerization to carry out end-blocking; Another kind method adds polarity modifier in the polymer, under the effect of radical initiator, carry out modification in chain.The shortcoming of terminal groups modification is that functionality is low, and selectable terminal groups modification agent is less, and raw materials pretreatment and product aftertreatment trouble; And the shortcoming of modification is that functionality is low in free radical chain, wayward, in modifying process, product is apt to deteriorate etc.
The halogenation of the inlay section thermal plastic multipolymer of vinylbenzene and conjugated diene carries out polar-modified effective means to it.After halogenation modification, the polarity of polymkeric substance increases, and its increase degree can increase along with the increase of halogenation degree.In addition, after halogenation modification, because carbon-halogen bond bond energy is lower, halogen easily removes, and therefore makes the further modification of polymkeric substance become possibility.
Because after the thermoplastic copolymer halogenation of vinylbenzene and conjugated diene, polarity increases, in order to increase the solvability of product, traditional halogenation is carried out in polar solvent.Polar solvent is generally selected from halogenated alkane or tetrahydrofuran (THF).E.BUZDUGAN (Eur.Polym.J.Vol.33, No.10-12, pp.1713-1716,1997) just have studied the bromination reaction carrying out SBS, SIS in tetrahydrofuran (THF).But in actual production, the solvent removal of styrene analog thermoplastic elastomer uses high-temperature steam to realize in agglomeration process, in this course, halogenated alkane is easy to hydrolysis and generates haloid acid, thus brings extreme difficulties to aftertreatment and solvent recuperation.And tetrahydrofuran (THF) is because water miscible feature, be also not suitable for traditional high-temperature steam removing process.
In the ternary block polymer of vinylbenzene, divinyl and isoprene, due to the existence be separated, multipolymer has multiple second-order transition temperature usually, one of them is the second-order transition temperature of hard section polystyrene block, this temperature is not generally by the impact of other factors, another is the second-order transition temperature of soft section of rubber phase, and this temperature is then by the impact of the factors such as component concentration, the microtexture of component, the block structure of component.But typically, under same preparation condition, the second-order transition temperature of the polyisoprene phase obtained is apparently higher than the second-order transition temperature of polyhutadiene phase.Therefore, along with isoprene content increases, in multipolymer, the second-order transition temperature of soft section of rubber phase raises.Because halogenating reaction is the addition reaction of halogen in soft section of rubber phase on carbon-to-carbon double bond, therefore the second-order transition temperature of polymkeric substance can improve along with the increase of addition structure.But, when styrene analog thermoplastic elastomer is applied to pressure sensitive adhesive, the second-order transition temperature (Tg) of its bond properties and base polymer has much relations, and the obvious rising of the second-order transition temperature of polymkeric substance can reduce the bond properties of tackiness agent.The object of halogenation be polarity by improving polymkeric substance to improve bond properties, and the negative results of polymer Tg increase can reduce the improvement effect of halogenation modification to bond properties.
The halogenating agent used during the thermoplastic copolymer halogenation of traditional vinylbenzene and conjugated diene is bromine or chlorine.The density of bromine is 3.12g/cm
3, much larger than the density of general polymers soln, which increase bromine dispersion difficulty in a polymer solution.Because the degree of unsaturation of the multipolymer of vinylbenzene and conjugated diene is very high, halogenating reaction speed is very fast, and therefore when incomplete mixing, polymkeric substance is easy to occur that halogenation is crossed in local, causes product variable color, sclerosis.Especially the halogenation in non-polar solvent, this problem is more serious.
In view of above-mentioned prior art situation, need to provide a kind of second-order transition temperature to raise unconspicuous halogenated styrenes analog thermoplastic elastomer, to improve the bond properties of the pressure sensitive adhesive of glue based on this polymkeric substance.
Summary of the invention
In view of above-mentioned condition of the prior art, the present inventor has carried out going deep into and studying widely at halogenated styrenes analog thermoplastic elastomer Material Field, to finding a kind of thermoplastic elastomer, this elastomerics not only obtains effective halogenation, and bond properties can be improved significantly when being applied in tackiness agent.Found that, occur in as far as possible isoprene monomer unit do not occur on butadiene monomer unit substantially by making the elastomeric halogenating reaction of the triblock copolymer of vinylbenzene, divinyl and isoprene and just can realize above-mentioned purpose.The present inventor completes the present invention based on above-mentioned discovery just.
Therefore, an object of the present invention is to provide the triblock copolymer of a kind of vinylbenzene of halogenation, divinyl and isoprene.This segmented copolymer is not only halogenated effectively, and makes the bond properties of tackiness agent significantly improve when being applied to pressure sensitive adhesive.
Another object of the present invention is to provide a kind of method preparing halogenation segmented copolymer of the present invention.
The technical scheme realizing above-mentioned purpose of the present invention can be summarized as follows:
1. a triblock copolymer for halogenation, this segmented copolymer before halogenation for having formula S
1-I/B-S
2the segmented copolymer of structure, wherein S
1and S
2be polystyrene block independently of one another, I/B represents the random copolymerization block of isoprene and divinyl, it is characterized in that, in halogenation segmented copolymer, in block I/B, contained by isoprene monomer unit, the 0.4-80% of unsaturated carbon-to-carbon double bond is halogenated, and in block I/B, the halogenation degree of unsaturated carbon-to-carbon double bond contained by butadiene monomer unit is no more than 0.01 with the ratio of the halogenation degree of carbon-to-carbon double bond unsaturated contained by isoprene monomer unit, and described halogenation is preferably bromination or chlorination.
2. the triblock copolymer of the halogenation according to the 1st, is characterized in that, in halogenation segmented copolymer, in block I/B, contained by isoprene monomer unit, the 3-75% of unsaturated carbon-to-carbon double bond is halogenated, and preferred 3-40% is halogenated.
3. the segmented copolymer of the halogenation according to the 1st or 2, wherein in halogenation segmented copolymer, in block I/B, the halogenation degree of unsaturated carbon-to-carbon double bond contained by butadiene monomer unit is no more than 0.005 with the ratio of the halogenation degree of carbon-to-carbon double bond unsaturated contained by isoprene monomer unit, and especially in block I/B, contained by butadiene monomer unit, unsaturated carbon-to-carbon double bond is not halogenated.
4. the triblock copolymer of the halogenation according to any one of 1-3 item, wherein the number-average molecular weight of halogenation segmented copolymer before halogenation is 5 × 10
4-50 × 10
4, preferably 5 × 10
4-30 × 10
4.
5. the triblock copolymer of the halogenation according to any one of 1-4 item, in segmented copolymer wherein before halogenation, based on the gross weight of the segmented copolymer before halogenation, styrenic monomer units content is 10-70 % by weight, butadiene monomer unit content is 10-80 % by weight, and isoprene monomer unit content is 10-80%; Preferably, styrenic monomer units content is 20-60 % by weight, and butadiene monomer unit content is 10-70 % by weight, and isoprene monomer unit content is 10-70 % by weight; It is further preferred that styrenic monomer units content is 20-40 % by weight, butadiene monomer unit content is 20-60 % by weight, and isoprene monomer unit content is 10-60%.
6. the triblock copolymer of the halogenation according to any one of 1-5 item, wherein S
1and S
2it is identical polystyrene block.
7. to prepare any one of 1-6 item a method for required halogenation triblock copolymer, comprise, before making halogenation, there is formula S
1-I/B-S
2the solution of the segmented copolymer of structure and halogenating agent react, and have formula S preferably before this halogenation of preparation
1-I/B-S
2the solvent that the solution of the segmented copolymer of structure uses is non-polar alkane, is preferably hexane, hexanaphthene, pentane, heptane or its mixture, is particularly preferably hexanaphthene.
8., according to the method for the 7th, wherein the add-on of halogenating agent should make this halogenating agent and formula S
1-I/B-S
2the mol ratio of the unsaturated carbon-to-carbon double bond in segmented copolymer contained by all isoprene monomer units is 0.01-1.0, is preferably 0.04-0.6.
9., according to the 7th or the method for 8, wherein halogenating agent is chlorine or bromine.
10. the method according to any one of 7-9 item, wherein the halogenating agent beyond dechlorination is diluted to halogenating agent content be after the solution of 0.2-25.0 % by weight, preferably 0.5-15.0 % by weight, particularly preferably 1.0-6.0 % by weight again with halogenation before there is formula S
1-I/B-S
2the solution reaction of the segmented copolymer of structure.
11. methods according to the 10th, the solvent wherein diluting halogenating agent use is non-polar alkane, be preferably hexane, hexanaphthene, pentane, heptane or its mixture, be particularly preferably hexanaphthene, especially dilute halogenating agent use solvent with preparation halogenation before there is formula S
1-I/B-S
2the solvent phase that the solution of the segmented copolymer of structure uses is same.
12. methods according to any one of 7-11 item, have formula S before wherein first synthesizing halogenation in a solvent
1-I/B-S
2the segmented copolymer of structure, obtains formula S
1-I/B-S
2the solution of segmented copolymer, just the solution of gained segmented copolymer and halogenating agent, the preferred halogenating agent diluted are reacted when not being separated this segmented copolymer, preferably synthesis has formula S
1-I/B-S
2the solvent that the segmented copolymer of structure uses is non-polar alkane, and being preferably hexane, hexanaphthene, pentane, heptane or its mixture, is especially hexanaphthene.
13. methods according to the 12nd, wherein synthesis has formula S
1-I/B-S
2the solvent that the segmented copolymer of structure uses is identical with dilution halogenating agent solvent for use.
Embodiment
According to an aspect of the present invention, provide a kind of triblock copolymer of halogenation, this segmented copolymer before halogenation for having formula S
1-I/B-S
2the segmented copolymer of structure, wherein S
1and S
2be polystyrene block (being sometimes referred to as block S below) independently of one another, I/B represents the random copolymerization block of isoprene and divinyl, it is characterized in that, in halogenation segmented copolymer, in isoprene monomer unit, the 0.4-80% of unsaturated carbon-to-carbon double bond is halogenated, and in butadiene monomer unit, the halogenation degree of unsaturated carbon-to-carbon double bond is no more than 0.01 with the ratio of the halogenation degree of unsaturated carbon-to-carbon double bond in isoprene monomer unit.
The triblock copolymer of vinylbenzene, divinyl and isoprene is a kind of thermoplastic elastic of excellent performance, and this elastomerics can be applicable to many fields, and particularly this thermoplastic elastomer can be used as the base material of tackiness agent.But this triblock copolymer does not conform to polar group, therefore blended with polar compound or there will be inconsistent problem when mixing, thus affect performance.By carrying out halogenation to this triblock copolymer, can greatly improve its polarity, thus improving the consistency between itself and polar compound, improving the bond properties of the pressure sensitive adhesive as base-material.
The present inventor's Late Cambrian, when the triblock copolymer of halogenated styrenes, divinyl and isoprene, if make halogenation occur in as far as possible on isoprene monomer unit substantially not occur on butadiene monomer unit, the triblock copolymer of gained halogenation not only can improve consistency effectively, and the rising of its second-order transition temperature is unlikely to too obvious, so that affect bond properties when being applied to pressure sensitive adhesive, the especially stripping strength of pressure sensitive adhesive.
As before halogenation segmented copolymer of the present invention halogenation, there is formula S
1-I/B-S
2the base block copolymer (sometimes also known as base copolymer or base block copolymer in the present invention) of structure, this multipolymer comprises three blocks, the random copolymerization block of isoprene and divinyl is positioned at centre, and two ends connect a polystyrene block respectively.Although S
1and S
2be respectively the polystyrene block be connected with the random copolymerization block of isoprene/butadiene, but these two blocks can exist difference about chain length, that is the length of these two blocks can be identical, also can be different.
For the purpose of the present invention, in halogenation segmented copolymer, usually have 0.4-80% to be halogenated in the unsaturated carbon-to-carbon double bond contained by isoprene monomer unit, preferably have 3-75% and be halogenated, more preferably 3-40% is halogenated.
To the present invention also importantly, in halogenation segmented copolymer, contained by butadiene monomer unit there is not halogenation in unsaturated carbon-to-carbon double bond substantially, be more specifically the halogenation degree of unsaturated carbon-to-carbon double bond contained by butadiene monomer unit (namely, the percentage ratio that in base block copolymer, contained by all butadiene monomer units, double bond is halogenated) with isoprene monomer unit contained by unsaturated carbon-to-carbon double bond halogenation degree (namely, the percentage ratio that in base block copolymer, contained by all isoprene monomer units, double bond is halogenated) ratio be no more than 0.01, preferably more than 0.005, especially contained by butadiene monomer unit, unsaturated carbon-to-carbon double bond is not halogenated.
In the present invention, halogenation is and makes vinylbenzene, divinyl be connected halogen atom with the triblock copolymer of isoprene with the form of chemical bond.As halogenation, be preferably chlorination or bromination.
In a preferred embodiment of the invention, the number-average molecular weight of halogenation segmented copolymer before halogenation is 5 × 10
4-50 × 10
4, preferably 5 × 10
4-30 × 10
4.In the present invention, all molecular weight related to all pass through gel permeation chromatography.
In another preferred embodiment of the present invention, in segmented copolymer before halogenation, based on the gross weight of the segmented copolymer before halogenation, styrenic monomer units content is 10-70 % by weight, butadiene monomer unit content is 10-80 % by weight, and isoprene monomer unit content is 10-80%; Preferably, styrenic monomer units content is 20-60 % by weight, and butadiene monomer unit content is 10-70 % by weight, and isoprene monomer unit content is 10-70%; It is further preferred that styrenic monomer units content is 20-40 % by weight, butadiene monomer unit content is 20-60 % by weight, and isoprene monomer unit content is 10-60%.
According to a further aspect in the invention, provide a kind of method preparing halogenation triblock copolymer of the present invention, comprise, before making halogenation, there is formula S
1-I/B-S
2the solution of the segmented copolymer of structure and halogenating agent react.
As preparation halogenation before there is formula S
1-I/B-S
2the solvent of the solution of the segmented copolymer of structure, preferably uses non-polar alkane, is more preferably hexane, hexanaphthene, pentane, heptane or its mixture, is particularly preferably hexanaphthene.
In order to obtain halogenation segmented copolymer of the present invention, advantageously, the consumption of halogenating agent should make this halogenating agent and formula S
1-I/B-S
2the mol ratio of the unsaturated carbon-to-carbon double bond in segmented copolymer contained by all isoprene monomer units is 0.01-1.0, is preferably 0.04-0.6.When halogenation, because in segmented copolymer, isoprene monomer unit is preferentially halogenated relative to butadiene monomer unit, therefore, under halogenating agent consumption of the present invention, halogenating reaction occurs substantially on isoprene monomer unit, and does not substantially occur on butadiene monomer unit.The second-order transition temperature of soft section of rubber phase can not raise too much not have the butadiene monomer unit of addition ensure that, like this, based on this polymkeric substance, the pressure sensitive adhesive of glue can not damage bond properties, the especially stripping strength of pressure sensitive adhesive because the second-order transition temperature of soft section of rubber phase raises too many.
In the present invention, as halogenating agent, preferably use chlorine or bromine.
Because the halogenating reaction speed of base block copolymer of the present invention and halogenating agent is very fast, therefore, when incomplete mixing, polymkeric substance is easy to occur that halogenation is crossed in local, causes product variable color, sclerosis, especially the halogenation in non-polar solvent, this problem is more serious.
When chlorine is as halogenating agent, advantageously with rare gas element, it is diluted, such as, use nitrogen dilution.When not changing those such as bromines of solute after halogenating agent is other with the solvent cut that can be used for halogenating reaction, useable solvents is diluted halogenating agent.
Therefore, in a particularly preferred embodiment of the present invention, by the halogenating agent beyond dechlorination as bromine be diluted to halogenating agent content be after the solution of 0.2-25.0 % by weight, preferably 0.5-15.0 % by weight, particularly preferably 1.0-6.0 % by weight again with halogenation before there is formula S
1-I/B-S
2the solution reaction of the segmented copolymer of structure.After dilution, concentration is too low, and a large amount of halogenating agents such as bromine is easily consumed by the reactive group in solvent, and meanwhile, a large amount of diluting solvents also can increase the load of aftertreatment; Excessive concentration after dilution, can increase again the risk that halogenation is crossed in polymkeric substance local.
As the solvent that the halogenating agent beyond dilution chlorine uses as bromine, preferably use non-polar alkane, be more preferably hexane, hexanaphthene, pentane, heptane or its mixture, be particularly preferably hexanaphthene.Further advantageously, dilute halogenating agent use solvent with preparation halogenation before there is formula S
1-I/B-S
2the solvent phase that the solution of the segmented copolymer of structure uses is same.Now, this solvent is advantageously selected from hexane, hexanaphthene, pentane, heptane or its mixture, is especially hexanaphthene.
Before halogenation, there is formula S
1-I/B-S
2the temperature of the solution of the segmented copolymer of structure and the halogenating reaction of halogenating agent has no particular limits, but usually should not be too high, is advisable with 0-60 DEG C.Halogenation temperature is too low, and polymer latex fluid viscosity is too large, and power consumption increases, and mixing difficulty also increases; Halogenation temperature is too high, and side reaction can obviously increase.
After halogenating reaction completes, add reductive agent and neutralizing agent.Reductive agent, for reducing residual halogenating agent, can be selected from sulphite or nitrite usually, as S-WAT, Sodium Pyrosulfite, Sodium Nitrite.The addition of reductive agent should make the halogenating agent remained be completely reduced usually.The addition of neutralizing agent should make to neutralize rear aqueous pH values and reach 8-10.Neutralizing agent is generally alkaline matter, as sodium hydroxide, potassium hydroxide etc., and preferred sodium hydroxide.Neutralizing agent also can be the salt of weak acid of basic metal or alkaline-earth metal, as sodium bicarbonate, and saleratus, sodium carbonate, salt of wormwood, calcium carbonate etc.After adding reductive agent and neutralizing agent, under admixture, add the auxiliary agent such as oxidation inhibitor, stablizer.Oxidation inhibitor is such as the Hinered phenols that rubber industry is conventional, as Irganox1010, Irganox1076, Irganox1330.Stablizer is such as epoxidized vegetable oil and stearate, as epoxy soybean oil and calcium stearate.
Namely reaction mixture after halogenation obtains finished product after desolvation, washing, drying.
In another preferred embodiment of the present invention, before first synthesizing halogenation in a solvent, there is formula S
1-I/B-S
2the segmented copolymer of structure, obtains formula S
1-I/B-S
2the solution of segmented copolymer, just reacts the solution of gained segmented copolymer and halogenating agent, the preferred halogenating agent diluted when not being separated this segmented copolymer.After polymerization obtains base polymer, in base polymer solution, directly add halogenating agent react, without the need to being separated from reaction mixture by base polymer, this greatly eliminates operation, and avoids the recycling of solvent.As synthesis, there is formula S
1-I/B-S
2the solvent of the segmented copolymer use of structure, preferably using non-polar alkane, be more preferably hexane, hexanaphthene, pentane, heptane or its mixture, is especially hexanaphthene.
In a particularly preferred embodiment of the present invention, synthesis has formula S
1-I/B-S
2the solvent that the segmented copolymer of structure uses is identical with dilution halogenating agent solvent for use.Now, this solvent is advantageously selected from hexane, hexanaphthene, pentane, heptane or its mixture, is especially hexanaphthene.The solvent that the solvent that halogenating reaction adopts is identical with the segmented copolymer of polymkeric substance based on preparation, can avoid solvent recovery problem.
In addition, in the application preparation method, when solvent adopts non-polar solvent, can avoid because of use polar solvent as halogenated alkane or tetrahydrofuran (THF) the recovery problem brought.
As three block base copolymer treating halogenation, it is prepared by ordinary method.This base polymer adopts anionic solution polymerization method to synthesize usually.Polymerization starter adopts lithium alkylide class initiator, and this comprises the monofunctional initiators such as n-Butyl Lithium, s-butyl lithium.Solvent uses nonpolar class alkane usually, as hexane, hexanaphthene, pentane, heptane, white oil or its mixture etc., also can use aromatic hydrocarbon solvent, as benzene, alkylbenzene etc.In addition, during copolymerization, depending on processing requirement, structure regulator can be added before polymerization or in polymerization process, structure regulator is also reactivity ratio of monomer conditioning agent usually, comprises some ethers and amine substance, as tetrahydrofuran (THF), ether, 2G, N, N, N ', N '-Tetramethyl Ethylene Diamine etc.Polymerization is carried out usually at 30-100 DEG C.Be polymerized complete, need to add terminator, as some alcohols materials, as methyl alcohol, Virahol etc., water also directly can be used as terminator.
In the present invention, add styrene monomer first in a solvent, then add monofunctional initiator.Depending on processing requirement, structure regulator can be added before polymerization or in polymerization process.After treating vinylbenzene complete reaction, add divinyl and isoprene monomer simultaneously.Treat that these two kinds of monomer complete reactions are complete, add remaining styrene monomer.React complete, add terminator termination reaction.
Embodiment
For a more detailed description to the present invention by embodiment below.These embodiments are all only to the description of the preferred embodiment of the invention, should not be construed as and have any restriction to protection scope of the present invention.
In following each embodiment and comparative example, before and after halogenation, the structural characterization of polymkeric substance uses BrukerAVANCE400MHz NMR spectrometer;
The second-order transition temperature of polymkeric substance adopts Pekin-Elmer DMA-7E dynamic visco-elasticity analyser to measure, frequency 1Hz, and temperature rise rate is 2 DEG C/min;
The stripping strength of pressure sensitive adhesive is according to GB-2792-81 standard test; The formula of pressure sensitive adhesive is as follows: rubber (segmented copolymer of non-halogenation or halogenation): 100 weight parts, hydrogenated petroleum resin: 170 weight parts, and naphthenic rubber process oil: 65 weight parts.
Comparative example 1
In 3L glass kettle, add solvent hexanaphthene 2000ml and styrene monomer 40g.The n-butyl lithium initiator 2.2ml that active lithium concentration is 1.0mol/L is added after using water bath with thermostatic control to make system be warmed up to 50 DEG C.After keeping water bath with thermostatic control 50 DEG C reaction 30min, add isoprene 36g and divinylic monomer 84g simultaneously.After keeping water bath with thermostatic control 50 DEG C reaction 50min, add styrene monomer 40g.After keeping water bath with thermostatic control 50 DEG C to continue reaction 30min, add terminator methyl alcohol 0.1ml, obtain polymers soln.Half polymers soln is proceeded to another 3L glass kettle, in that remaining half polymers soln, add 0.2g antioxidant 1010.Namely the polymer product of non-halogenation will be obtained after that half polymkeric substance desolvation adding oxidation inhibitor.The number-average molecular weight of products therefrom is 10.2 × 10
4, other stuctures and properties is in table 1.
Embodiment 2
When that half polymer solution temperature proceeded in 3L glass kettle described in comparative example 1 drops to 30 DEG C, add the solution of 20.4g bromine in 400g hexanaphthene under vigorous stirring, under non-lucifuge condition, halogenating reaction occurs.After reaction 5min, add the metabisulfite solution 50ml that aqueous sodium hydroxide solution 250ml that concentration is 1.0mol/L and concentration are 1.0mol/L.After continuing to stir 10min, add calcium stearate and each 2.0g of epoxy soybean oil, and 0.2g antioxidant 1010, obtain polymers soln.Be neutral by resulting polymers solution deionized water repetitive scrubbing to pH, after desolvation, namely obtain halogenated polymer product.The stuctures and properties of products therefrom is in table 1.
Comparative example 3
In 3L glass kettle, add solvent hexanaphthene 2000ml and styrene monomer 20g, and concentration is the THF cyclohexane solution 10ml of 1.0mol/L.The n-butyl lithium initiator 1.4ml that active lithium concentration is 1.0mol/L is added after using water bath with thermostatic control to make system be warmed up to 50 DEG C.After keeping water bath with thermostatic control 50 DEG C reaction 30min, add isoprene 112g and divinylic monomer 48g simultaneously.After keeping water bath with thermostatic control 50 DEG C reaction 50min, add styrene monomer 20g.After keeping water bath with thermostatic control 50 DEG C to continue reaction 30min, add terminator methyl alcohol 0.1ml, obtain polymers soln.Half polymers soln is proceeded to another 3L glass kettle, in that remaining half polymers soln, add 0.2g antioxidant 1010.Namely the polymer product of non-halogenation will be obtained after that half polymers soln desolvation adding oxidation inhibitor.The number-average molecular weight of products therefrom is 15.3 × 10
4, other stuctures and properties is in table 1.
Embodiment 4
When that half polymer solution temperature proceeded in 3L glass kettle described in comparative example 3 drops to 30 DEG C, add the solution of 6.6g bromine in 20g hexanaphthene under vigorous stirring, under non-lucifuge condition, halogenating reaction occurs.After reaction 5min, add the metabisulfite solution 50ml that aqueous sodium hydroxide solution 250ml that concentration is 1.0mol/L and concentration are 1.0mol/L.After continuing to stir 10min, add calcium stearate and each 2.0g of epoxy soybean oil, and 0.2g antioxidant 1010, obtain polymers soln.Be neutral by resulting polymers solution deionized water repetitive scrubbing to pH, after desolvation, namely obtain halogenated polymer product.The stuctures and properties of products therefrom is in table 1.
Comparative example 5
In 3L glass kettle, add solvent hexanaphthene 2000ml and styrene monomer 30g.The n-butyl lithium initiator 2.2ml that active lithium concentration is 1.0mol/L is added after using water bath with thermostatic control to make system be warmed up to 50 DEG C.After keeping water bath with thermostatic control 50 DEG C reaction 30min, add divinylic monomer 116g and isoprene monomer 24g.After keeping water bath with thermostatic control 50 DEG C reaction 50min, add styrene monomer 30g.After keeping water bath with thermostatic control 50 DEG C to continue reaction 30min, add terminator methyl alcohol 0.1ml, obtain polymers soln.Half polymers soln is proceeded to another 3L glass kettle, in that remaining half polymers soln, add 0.2g antioxidant 1010.Namely the polymer product of non-halogenation will be obtained after that half polymers soln desolvation adding oxidation inhibitor.The number-average molecular weight of products therefrom is 9.8 × 10
4, other stuctures and properties is in table 1.
Embodiment 6
When that half polymer solution temperature proceeded in 3L glass kettle described in comparative example 5 drops to 30 DEG C, add the solution of 28.2g bromine in 200g hexanaphthene under vigorous stirring, under non-lucifuge condition, halogenating reaction occurs.After reaction 5min, add the metabisulfite solution 50ml that aqueous sodium hydroxide solution 300ml that concentration is 1.0mol/L and concentration are 1.0mol/L.After continuing to stir 10min, add calcium stearate and each 2.0g of epoxy soybean oil, and 0.2g antioxidant 1010, obtain polymers soln.Be neutral by resulting polymers solution deionized water repetitive scrubbing to pH, after desolvation, namely obtain halogenated polymer product.The stuctures and properties of products therefrom is in table 1.
Comparative example 7
In 5L glass kettle, add solvent hexanaphthene 3000ml and styrene monomer 60g.The n-butyl lithium initiator 3.2ml that active lithium concentration is 1.0mol/L is added after using water bath with thermostatic control to make system be warmed up to 50 DEG C.After keeping water bath with thermostatic control 50 DEG C reaction 30min, add isoprene 54g and divinylic monomer 126g.After keeping water bath with thermostatic control reaction 50min, add styrene monomer 60g.After keeping water bath with thermostatic control 50 DEG C to continue reaction 30min, add terminator methyl alcohol 0.1ml, obtain polymers soln.2/3 polymers soln is proceeded to another two 3L glass kettles and be used for halogenation, in each still, proceed to 1/3 polymers soln, in 1/3 remaining polymers soln, add 0.2g antioxidant 1010.Namely the polymer product of non-halogenation will be obtained after that the 1/3 polymers soln desolvation adding oxidation inhibitor.The number-average molecular weight of products therefrom is 10.2 × 10
4, other stuctures and properties is in table 1.
Embodiment 8
When portion 1/3 polymer solution temperature proceeded to described in comparative example 7 drops to 30 DEG C, add the solution of 0.42g bromine in 30g hexanaphthene under vigorous stirring, under non-lucifuge condition, halogenating reaction occurs.After reaction 5min, add the metabisulfite solution 50ml that aqueous sodium hydroxide solution 250ml that concentration is 1.0mol/L and concentration are 1.0mol/L, after continuing to stir 10min, add calcium stearate and each 2.0g of epoxy soybean oil, with 0.2g antioxidant 1010, obtain polymers soln.Be neutral by resulting polymers solution deionized water repetitive scrubbing to pH, after desolvation, namely obtain the polymer product of halogenation.The structure of products therefrom and performance are in table 1.
Comparative example 9
When another 1/3 polymer solution temperature proceeded to described in comparative example 7 drops to 30 DEG C, add the solution of 52.1g bromine in 850g hexanaphthene under vigorous stirring, under non-lucifuge condition, halogenating reaction occurs.After reaction 5min, add the metabisulfite solution 100ml that aqueous sodium hydroxide solution 500ml that concentration is 1.0mol/L and concentration are 1.0mol/L, after continuing to stir 10min, add calcium stearate and each 2.0g of epoxy soybean oil, with 0.2g antioxidant 1010, obtain polymers soln.Be neutral by resulting polymers solution deionized water repetitive scrubbing to pH, after desolvation, namely obtain the polymer product of halogenation.The structure of products therefrom and performance are in table 1.This polymkeric substance is no longer suitable for pressure sensitive adhesive.
The structure of product and performance before and after table 1. bromination
From table 1 embodiment 2,4,6,8 result viewed from, when halogenation degree is suitable, before and after halogenation, the Tg change of polymer rubber phase is little, illustrates that halogenation is very little to the negative impact of rubber phase.By contrast, because the polarity of material after halogenation increases, based on halogenated polymer, the stripping strength of the pressure sensitive adhesive of glue obviously increases.
Comparative example 10
Repeat embodiment 2, difference is: the 400g hexanaphthene that dilution 20.4g bromine uses is kept to 50g hexanaphthene, and bromine weaker concn is 29.0%.In halogenation process, observe a large amount of polymkeric substance and be wrapped on stir shaft, cannot be separated, neutralize and wash.After drying, polymer hardens, color becomes redness, cannot be used for pressure sensitive adhesive.
Claims (13)
1. a triblock copolymer for halogenation, this segmented copolymer before halogenation for having formula S
1-I/B-S
2the segmented copolymer of structure, wherein S
1and S
2be polystyrene block independently of one another, I/B represents the random copolymerization block of isoprene and divinyl, it is characterized in that, in halogenation segmented copolymer, in block I/B, contained by isoprene monomer unit, the 0.4-80% of unsaturated carbon-to-carbon double bond is halogenated, and in block I/B, the halogenation degree of unsaturated carbon-to-carbon double bond contained by butadiene monomer unit is no more than 0.01 with the ratio of the halogenation degree of carbon-to-carbon double bond unsaturated contained by isoprene monomer unit, and described halogenation is preferably bromination or chlorination.
2. the triblock copolymer of halogenation according to claim 1, is characterized in that, in halogenation segmented copolymer, in block I/B, contained by isoprene monomer unit, the 3-75% of unsaturated carbon-to-carbon double bond is halogenated, and preferred 3-40% is halogenated.
3. the segmented copolymer of halogenation according to claim 1 and 2, wherein in halogenation segmented copolymer, in block I/B, the halogenation degree of unsaturated carbon-to-carbon double bond contained by butadiene monomer unit is no more than 0.005 with the ratio of the halogenation degree of carbon-to-carbon double bond unsaturated contained by isoprene monomer unit, and especially in block I/B, contained by butadiene monomer unit, unsaturated carbon-to-carbon double bond is not halogenated.
4. the triblock copolymer of the halogenation according to any one of claim 1-3, wherein the number-average molecular weight of halogenation segmented copolymer before halogenation is 5 × 10
4-50 × 10
4, preferably 5 × 10
4-30 × 10
4.
5. the triblock copolymer of the halogenation according to any one of claim 1-4, in segmented copolymer wherein before halogenation, based on the gross weight of the segmented copolymer before halogenation, styrenic monomer units content is 10-70 % by weight, butadiene monomer unit content is 10-80 % by weight, and isoprene monomer unit content is 10-80%; Preferably, styrenic monomer units content is 20-60 % by weight, and butadiene monomer unit content is 10-70 % by weight, and isoprene monomer unit content is 10-70 % by weight; It is further preferred that styrenic monomer units content is 20-40 % by weight, butadiene monomer unit content is 20-60 % by weight, and isoprene monomer unit content is 10-60%.
6. the triblock copolymer of the halogenation according to any one of claim 1-5, wherein S
1and S
2it is identical polystyrene block.
7. to prepare any one of claim 1-6 a method for required halogenation triblock copolymer, comprise, before making halogenation, there is formula S
1-I/B-S
2the solution of the segmented copolymer of structure and halogenating agent react, and have formula S preferably before this halogenation of preparation
1-I/B-S
2the solvent that the solution of the segmented copolymer of structure uses is non-polar alkane, is preferably hexane, hexanaphthene, pentane, heptane or its mixture, is particularly preferably hexanaphthene.
8. method according to claim 7, wherein the add-on of halogenating agent should make this halogenating agent and formula S
1-I/B-S
2the mol ratio of the unsaturated carbon-to-carbon double bond in segmented copolymer contained by all isoprene monomer units is 0.01-1.0, is preferably 0.04-0.6.
9., according to the method for claim 7 or 8, wherein halogenating agent is chlorine or bromine.
10. the method according to any one of claim 7-9, wherein the halogenating agent beyond dechlorination is diluted to halogenating agent content be after the solution of 0.2-25.0 % by weight, preferably 0.5-15.0 % by weight, particularly preferably 1.0-6.0 % by weight again with halogenation before there is formula S
1-I/B-S
2the solution reaction of the segmented copolymer of structure.
11. methods according to claim 10, the solvent wherein diluting halogenating agent use is non-polar alkane, be preferably hexane, hexanaphthene, pentane, heptane or its mixture, be particularly preferably hexanaphthene, especially dilute halogenating agent use solvent with preparation halogenation before there is formula S
1-I/B-S
2the solvent phase that the solution of the segmented copolymer of structure uses is same.
12. methods according to any one of claim 7-11, have formula S before wherein first synthesizing halogenation in a solvent
1-I/B-S
2the segmented copolymer of structure, obtains formula S
1-I/B-S
2the solution of segmented copolymer, just the solution of gained segmented copolymer and halogenating agent, the preferred halogenating agent diluted are reacted when not being separated this segmented copolymer, preferably synthesis has formula S
1-I/B-S
2the solvent that the segmented copolymer of structure uses is non-polar alkane, and being preferably hexane, hexanaphthene, pentane, heptane or its mixture, is especially hexanaphthene.
13. methods according to claim 12, wherein synthesis has formula S
1-I/B-S
2the solvent that the segmented copolymer of structure uses is identical with dilution halogenating agent solvent for use.
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| CN110511300A (en) * | 2019-09-18 | 2019-11-29 | 青岛科技大学 | A kind of trans- butadiene-isoprene copolymer glue of halogenation and its preparation method and application |
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