CN104592465B - A kind of many blocks halogen polymer and preparation method thereof - Google Patents
A kind of many blocks halogen polymer and preparation method thereof Download PDFInfo
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- CN104592465B CN104592465B CN201310522018.3A CN201310522018A CN104592465B CN 104592465 B CN104592465 B CN 104592465B CN 201310522018 A CN201310522018 A CN 201310522018A CN 104592465 B CN104592465 B CN 104592465B
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Abstract
The present invention relates to a kind of halogenation segmented copolymer, the block copolymer before halogenation be with formula S1‑B1‑I‑B2‑S2The block copolymer of structure, wherein S1And S2It is each independently polystyrene block, B1And B2Polybutadiene block is each independently, and I is polyisoprene blocks, wherein in halogenation block copolymer, the 0.4 80% of unsaturated carbon-carbon double bond contained by block I is by halogenation, and B block1And B2The halogenation degree of contained unsaturation carbon-carbon double bond is less than 0.01 with the ratio of the halogenation degree of unsaturated carbon-carbon double bond contained by block I.The invention further relates to the method for preparing halogenation segmented copolymer of the present invention.Halogenation segmented copolymer of the present invention can not only effectively improve its compatibility with other polar polymers, and the rising of its vitrification point is less obvious, so that affecting the peel strength of bond properties, especially pressure sensitive adhesive when being applied to contact adhesive.
Description
Technical field
The present invention relates to a kind of halogenation segmented copolymer.More particularly it relates to a kind of styrene, butadiene
Halide with five block copolymers of isoprene.The invention additionally relates to prepare the side of the halogenation segmented copolymer
Method.
Background technology
Conjugated diene-styrene block copolymer generally includes SBS, SIS etc., and this kind of polymer is frequently used for bonding
Agent, plastic modifier, asphalt modifier etc..Due in the application, being easily crosslinked when SBS is heated and increasing melt viscosity, and
SIS then easily goes bad because of degraded, therefore have developed in recent years the tri-block of a kind of styrene, butadiene and isoprene altogether
Polymers is to overcome both polymer produced problem in the application.But as this kind of polymer polarity is relatively low, in these occasions
It is frequently necessary to during application through polar-modified, to improve their bond properties or compatibility performance.Method of modifying includes that end group changes
Property, it is common practice to add polarity modifier to be blocked after completion of polymerization；Another kind of method is to add in the polymer
Polarity modifier, is carried out modified in chain in the presence of radical initiator.The shortcoming of terminal groups modification is that degree of functionality is low, may be selected
Terminal groups modification agent less, and pretreatment of raw material and product post processing trouble；And modified in free radical chain have the disadvantage sense
Degree is low, wayward, and in modifying process, product is apt to deteriorate etc..
Styrene is to carry out polar-modified effective hand to which with the halogenation of the inlay section thermal plastic copolymer of conjugated diene
Section.After halogenation modification, the polarity of polymer increases, and its increase degree can increase with the increase of halogenation degree.Separately
Outward, after halogenation modification, as carbon-halogen bond bond energy is relatively low, halogen is easily removed, and therefore makes being modified to further for polymer
For possibility.
As after thermoplastic copolymer halogenation of the styrene with conjugated diene, polarity increases, in order to increase the dissolving of product
Property, traditional halogenation is carried out in polar solvent.Polar solvent is selected generally from halogenated alkane or tetrahydrofuran.E.BUZDUGAN
(Eur.Polym.J.Vol.33, No.10-12, pp.1713-1716,1997) just have studied carry out in tetrahydrofuran SBS,
The bromination reaction of SIS.But in actual production, the solvent removal of styrene analog thermoplastic elastomer is made in coacervation process
Realized with high-temperature steam, in this course, halogenated alkane is easy to hydrolysis and generates halogen acids, post-processes and molten so as to give
Agent is reclaimed and brings extreme difficulties.And tetrahydrofuran is also not suitable for traditional high-temperature steam removing process because water miscible feature.
In the ternary block polymer of styrene, butadiene and isoprene, due to the presence being separated, copolymer leads to
Often there are multiple glass transition temperatures, one of them is the glass transition temperature of hard section polystyrene block, this temperature one
As do not affected by other factorses, another is the glass transition temperature of soft section rubber phase, the temperature then receive constituent content, group
Point microstructure, the impact of the factor such as the block structure of component.But it is typically, under same preparation condition, obtained
Polyisoprene phase glass transition temperature apparently higher than polybutadiene phase glass transition temperature.Therefore, with different
Pentadiene content increases, and in copolymer, the vitrification point of soft section rubber phase is raised.As halogenation is halogen in soft section rubber
Addition reaction in glue phase on carbon-to-carbon double bond, therefore the glass transition temperature of polymer can be with the increase of addition structure
Improve.However, when styrene analog thermoplastic elastomer is applied to contact adhesive, the glass of its bond properties and base polymer
Glass transition temperature (Tg) has much relations, the significantly raised bonding that can reduce adhesive of the glass transition temperature of polymer
Performance.The purpose of halogenation is and the negative results that polymer Tg increases by improving the polarity of polymer to improve bond properties
Improvement of the halogenation modification to bond properties can be reduced.
The halogenating agent used during the thermoplastic copolymer halogenation of traditional styrene Yu conjugated diene is bromine or chlorine.
The density of bromine is 3.12g/cm3, much larger than the density of general polymer solution, which increase bromine in a polymer solution
Dispersion difficulty.As styrene is very high with the degree of unsaturation of the copolymer of conjugated diene, halogenation speed quickly, therefore
In the case of incomplete mixing, polymer is easy to be occurred locally crossing halogenation, causes product discoloration, hardening.Especially in non-pole
Halogenation in property solvent, this problem are more serious.
In view of above-mentioned prior art situation, it is desirable to provide a kind of glass transition temperature raises unconspicuous halogenated styrenes
Analog thermoplastic elastomer, by the bond properties for improving the contact adhesive of glue based on this polymer.
Content of the invention
In view of above-mentioned condition of the prior art, the present inventor is in halogenated styrenes analog thermoplastic elastomer material
Field has carried out deeply and widely studying, and to finding a kind of thermoplastic elastomer (TPE), the elastomer is not only obtained effectively
Halogenation, and when being applied in adhesive, bond properties can be improved significantly.As a result find, by making styrene, fourth two
The halogenation of the segmented copolymer elastomer of alkene and isoprene occurs on isoprene monomer unit and base as far as possible
Do not occur just realize above-mentioned purpose on butadiene monomer unit in sheet.The present inventor is based on above-mentioned discovery and completes
The present invention.
Therefore, it is an object of the present invention to provide many blocks of a kind of styrene of halogenation, butadiene and isoprene
Copolymer, especially their five block copolymers.The segmented copolymer is not only effectively by halogenation, and ought be applied to pressure
Significantly improve the bond properties of adhesive during sensitive adhesive.
It is a further object to provide a kind of method for preparing halogenation segmented copolymer of the present invention.
The technical scheme for realizing above-mentioned purpose of the present invention can be summarized as follows：
1. a kind of segmented copolymer of halogenation, the block copolymer before halogenation be with formula S1-B1-I-B2-S2Structure
Block copolymer, wherein S1And S2It is each independently polystyrene block, B1And B2It is each independently polybutadiene embedding
Section, and I is polyisoprene blocks, it is characterised in that in halogenation block copolymer, unsaturated carbon-to-carbon contained by block I pair
The 0.4-80% of key is by halogenation, and B block1And B2The halogenation degree of contained unsaturation carbon-to-carbon double bond and insatiable hunger contained by block I
0.01 is less than with the ratio of the halogenation degree of carbon-to-carbon double bond, the halogenation is preferably bromination or chlorination.
2. the segmented copolymer of the halogenation according to the 1st, it is characterised in that in halogenation block copolymer, embedding
, by halogenation, preferably 3-40% is by halogenation for the 3-75% of the unsaturated carbon-to-carbon double bond contained by section I.
3. the segmented copolymer of the halogenation according to the 1st or 2, wherein in halogenation block copolymer, B block1
And B2The halogenation degree of contained unsaturation carbon-to-carbon double bond and unsaturated carbon contained by block I-The ratio of the halogenation degree of carbon double bond does not surpass
0.005 is crossed, especially B block1And B2Contained unsaturation carbon-to-carbon double bond is not by halogenation.
4. the segmented copolymer of the halogenation according to any one of 1-3 item, wherein halogenation block copolymer is in halogen
Number-average molecular weight before change is 5 × 104-50×104, preferably 5 × 104-30×104.
5. the segmented copolymer of the halogenation according to any one of 1-4 item, the wherein block copolymerization before halogenation
In thing, based on the gross weight of the block copolymer before halogenation, styrenic monomer units content is 10-70 weight %, butadiene list
Body unit content is 10-80 weight %, and isoprene monomer unit content is 10-80%；Preferably, styrene monomer list
First content is 20-60 weight %, and butadiene monomer unit content is 10-70 weight %, and isoprene monomer unit content is
10-70 weight %；It is further preferred that styrenic monomer units content is 20-40 weight %, butadiene monomer unit content is
20-60 weight %, and isoprene monomer unit content be 10-60%.
6. the segmented copolymer of the halogenation according to any one of 1-5 item, wherein S1And S2It is identical polyphenyl second
Alkene block, and/or, B1And B2It is identical polybutadiene block.
7. a kind of method of the halogenation segmented copolymer prepared as required by any one of 1-6 item, including making halogenation
Front formula S1-B1-I-B2-S2The solution of the block copolymer of structure is reacted with halogenating agent, preferably prepares formula S before the halogenation1-
B1-I-B2-S2The solvent that the solution of the block copolymer of structure is used be non-polar alkane, preferably hexane, hexamethylene, pentane,
Heptane or its mixture, particularly preferably hexamethylene.
8., according to the method for the 7th, wherein the addition of halogenating agent should cause the halogenating agent and formula S1-B1-I-B2-S2Embedding
In section copolymer, contained by all isoprene monomer units, the mol ratio of unsaturated carbon-to-carbon double bond is 0.01-1.0, preferably
0.04-0.6, more preferably 0.2-0.5.
9., according to the method for the 7th or 8, wherein halogenating agent is chlorine or bromine.
10. the halogenating agent beyond dechlorination is wherein diluted to halogenating agent and contains by the method according to any one of 7-9 item
Measure for after 0.2-25.0 weight %, preferred 0.5-15.0 weight %, the solution of particularly preferred 1.0-6.0 weight % again with halogenation before
Formula S1-B1-I-B2-S2The solution reaction of the block copolymer of structure.
11. methods according to the 10th, the wherein solvent that uses of dilution halogenating agent are non-polar alkane, preferably oneself
Alkane, hexamethylene, pentane, heptane or its mixture, particularly preferably hexamethylene, solvent and system that especially dilution halogenating agent is used
Formula S before standby halogenation1-B1-I-B2-S2The solvent that the solution of the block copolymer of structure is used is identical.
12. methods according to any one of 7-11 item, wherein first synthesize formula S before halogenation in a solvent1-B1-I-
B2-S2The block copolymer of structure, obtains formula S1-B1-I-B2-S2The solution of block copolymer, is not separating the block copolymer
In the case of just the solution of gained block copolymer is reacted with halogenating agent, the halogenating agent for preferably diluting, preferably synthetic formula
S1-B1-I-B2-S2The solvent that the block copolymer of structure is used is non-polar alkane, preferably hexane, hexamethylene, pentane, heptan
Alkane or its mixture, in particular hexamethylene.
13. methods according to the 12nd, wherein synthesis type S1-B1-I-B2-S2The block copolymer of structure is used
Solvent is identical with dilution halogenating agent solvent for use.
Specific embodiment
According to an aspect of the invention, there is provided a kind of segmented copolymer of halogenation, the block copolymer is in halogenation
Before be with formula S1-B1-I-B2-S2The block copolymer of structure, wherein S1And S2It is each independently polystyrene block (below
Sometimes it is referred to as block S), B1And B2Polybutadiene block (being referred to as sometimes B block below) is each independently, and I is poly- isoamyl two
Alkene block, it is characterised in that in halogenation block copolymer, the 0.4-80% of the unsaturated carbon-to-carbon double bond contained by block I is by halogen
Change, and B block1And B2The halogenation degree of contained unsaturation carbon-to-carbon double bond and the halogenation of unsaturated carbon-to-carbon double bond contained by block I
The ratio of degree is less than 0.01.
Five block copolymers of styrene, butadiene and isoprene are a kind of thermoplastic elastic of excellent performance, the bullet
Gonosome can be applicable to many fields, be particularly the base material that the thermoplastic elastomer (TPE) can be used as adhesive.However, five block
Copolymer not polar functionalities, therefore occur incompatible problem when being blended with polar compound or mixing, so as to impact property
Energy.By halogenation being carried out to five block copolymer, be greatly improved its polarity, so as to improve its phase between polar compound
Capacitive, improves the bond properties of the contact adhesive as base-material.
The present inventor has found first, in five block copolymer of halogenated styrenes, butadiene and isoprene,
If making halogenation occur as far as possible in polyisoprene blocks and substantially not occur on polybutadiene block, gained halogenation
Five block copolymers not only can effectively improve compatibility, and the rising of its vitrification point be unlikely to too substantially, with
Cause the peel strength of bond properties, especially pressure sensitive adhesive when impact is applied to contact adhesive.
(sometimes also known as basic in the present invention as the base block copolymer before halogenation block copolymer halogenation of the present invention
Copolymer or base block copolymer), the copolymer includes five blocks, and isoprene block is located at centre, and isoprene is embedding
The two ends of section reconnect a polybutadiene block respectively, and two polybutadiene blocks to connect a polystyrene again respectively embedding
Section.Although B1And B2The polybutadiene block being connected with isoprene is, but the two blocks there may be difference with regard to chain length
Not, that is to say, that the length of the two blocks can be identical, it is also possible to which different, preferably they have identical chain length.Equally, to the greatest extent
Pipe S1And S2The polystyrene block being respectively connected with two polybutadiene blocks, but the two blocks are permissible with regard to chain length
There is difference, that is to say, that the length of the two blocks can be identical, it is also possible to different.
For the purpose of the present invention, in halogenation block copolymer, in the unsaturated carbon-to-carbon double bond contained by polyisoprene blocks
Generally there is 0.4-80% by halogenation, preferably have 3-75% by halogenation, more preferably 3-40% is by halogenation.
To the present invention it is also important that, in halogenation block copolymer, B block1And B2Contained unsaturation carbon-to-carbon double bond base
There is no halogenation in sheet, be more specifically B block1And B2Halogenation degree (that is, the base block of contained unsaturation carbon-to-carbon double bond
In copolymer, double bond contained by all butadiene monomer units is by the percentage of halogenation) and unsaturated carbon-to-carbon double bond contained by block I
The ratio of halogenation degree (that is, double bond contained by all isoprene monomer units is by the percentage of halogenation in base block copolymer) is not
More than 0.01, contained by preferably more than 0.005, especially B block, unsaturated carbon-to-carbon double bond is not by halogenation.
In the present invention, halogenation as makes five block copolymers of styrene, butadiene and isoprene with chemical bond
The upper halogen atom of form connection.As halogenation, preferably chlorination or bromination.
In a preferred embodiment of the invention, number-average molecular weight of the halogenation block copolymer before halogenation be 5 ×
104-50×104, preferably 5 × 104-30×104.In the present invention, all molecular weight being related to all pass through gel permeation chromatography
Determine.
In another preferred embodiment of the present invention, in the block copolymer before halogenation, based on the block before halogenation
The gross weight of copolymer, styrenic monomer units content are 10-70 weight %, and butadiene monomer unit content is 10-80 weight
% is measured, and isoprene monomer unit content is 10-80%；Preferably, styrenic monomer units content is 20-60 weight
Amount %, butadiene monomer unit content are 10-70 weight %, and isoprene monomer unit content is 10-70%；More preferably
It is that styrenic monomer units content is 20-40 weight %, butadiene monomer unit content is 20-60 weight %, and isoprene
Monomer unit content is 10-60%.
According to a further aspect in the invention, there is provided a kind of method of the halogenation segmented copolymer for preparing the present invention, wrap
Include formula S before making halogenation1-B1-I-B2-S2The solution of the block copolymer of structure is reacted with halogenating agent.
As formula S prepared before halogenation1-B1-I-B2-S2The solvent of the solution of the block copolymer of structure, preferably uses non-
Polarity alkane, more preferably hexane, hexamethylene, pentane, heptane or its mixture, particularly preferably hexamethylene.
In order to obtain the halogenation block copolymer of the present invention, it is advantageous to the consumption of halogenating agent should cause the halogenating agent with
Formula S1-B1-I-B2-S2The mol ratio of the unsaturated carbon-to-carbon double bond in block copolymer contained by all isoprene monomer units is
0.01-1.0, preferably 0.04-0.6.In halogenation, due in block copolymer isoprene monomer unit with respect to butadiene
, preferentially by halogenation, therefore under the halogenating agent consumption of the present invention, halogenation is substantially in polyisoprene blocks for monomeric unit
Upper generation, and substantially do not occur on polybutadiene block.Polybutadiene block without addition ensure that soft section rubber phase
Glass transition temperature will not raise too much, so, based on this polymer, the contact adhesive of glue will not be because of soft section
The vitrification point of rubber phase raises peel strength that is too many and damaging bond properties, especially pressure sensitive adhesive.
In the present invention, as halogenating agent, chlorine or bromine is preferably used.
Due to the present invention base block copolymer and halogenating agent halogenation speed quickly, therefore in incomplete mixing
In the case of, polymer is easy to be occurred locally crossing halogenation, causes product discoloration, especially hardening, the halogen in non-polar solven
Change, this problem is more serious.
When chlorine is used as halogenating agent, advantageously which is diluted with inert gas, for example, is diluted with nitrogen.Work as halogenation
When agent is those the such as bromines for not changing solute with the solvent that can be used for halogenation after other are diluted, can be with solvent to halogenating agent
It is diluted.
Therefore, in a particularly preferred embodiment of the present invention, the such as bromine of the halogenating agent beyond dechlorination is diluted to
Halogenation agent content is 0.2-25.0 weight %, preferred 0.5-15.0 weight %, after the solution of particularly preferred 1.0-6.0 weight % again
With formula S before halogenation1-B1-I-B2-S2The solution reaction of the block copolymer of structure.After dilution, concentration is too low, substantial amounts of halogenation
Agent as bromine easily by the reactive group consumption in solvent, meanwhile, substantial amounts of retarder thinner can also increase the load of post processing；Dilution
Excessive concentration, can increase the risk that halogenation is crossed in polymer local again afterwards.
As the solvent that uses of halogenating agent such as bromine beyond dilution chlorine, preferably use non-polar alkane, more preferably oneself
Alkane, hexamethylene, pentane, heptane or its mixture, particularly preferably hexamethylene.It is further advantageous that what dilution halogenating agent was used
Solvent and formula S prepared before halogenation1-B1-I-B2-S2The solvent that the solution of the block copolymer of structure is used is identical.Now, should
Solvent is advantageously selected from hexane, hexamethylene, pentane, heptane or its mixture, in particular hexamethylene.
Formula S before halogenation1-B1-I-B2-S2The solution of the block copolymer of structure and the temperature of the halogenation of halogenating agent
Have no particular limits, but generally should not be too high, it is advisable with 0-60 DEG C.Halogenation temperature is too low, and polymer latex fluid viscosity is too big, consumption
Can increase, mixing difficulty also increases；Halogenation temperature is too high, and side reaction substantially can increase.
After the completion of halogenation, reducing agent and nertralizer is added.Reducing agent is used for reducing the halogenating agent of residual, generally may be used
Selected from sulphite or nitrite, such as sodium sulfite, sodium pyrosulfite, natrium nitrosum.The addition of reducing agent should generally make
The halogenating agent that must be remained is completely reduced.After the addition of nertralizer should cause neutralization, aqueous pH values reach 8-10.Nertralizer one
As be alkaline matter, such as NaOH, potassium hydroxide etc., preferably NaOH.Nertralizer can also be alkali metal or alkaline earth gold
The salt of weak acid of category, such as sodium acid carbonate, saleratus, sodium carbonate, potassium carbonate, calcium carbonate etc..After adding reducing agent and nertralizer,
The auxiliary agents such as antioxidant, stabilizer are added under admixture.Antioxidant is, for example, the conventional Hinered phenols of rubber industry, such as
Irganox1010、Irganox1076、Irganox1330.Stabilizer for example, epoxidized vegetable oil and stearate, such as epoxy are big
Soya-bean oil and calcium stearate.
Reactant mixture after halogenation obtains finished product through desolvation, washing, after drying.
In another preferred embodiment of the present invention, first synthesize formula S before halogenation in a solvent1-B1-I-B2-S2Structure
Block copolymer, obtain formula S1-B1-I-B2-S2The solution of block copolymer, in the case of the block copolymer is not separated
Just the solution of gained block copolymer is reacted with halogenating agent, the halogenating agent for preferably diluting.Base polymer is obtained in polymerization
After thing, in base polymer solution, halogenating agent is directly added to be reacted, without the need for by base polymer from reactant mixture
Separate, this greatly eliminates operation, and avoids the recycling of solvent.As synthesis type S1-B1-I-B2-S2Structure
The solvent that uses of block copolymer, preferably use non-polar alkane, more preferably hexane, hexamethylene, pentane, heptane or which is mixed
Compound, in particular hexamethylene.
In a particularly preferred embodiment of the present invention, synthesis type S1-B1-I-B2-S2The block copolymer of structure makes
Solvent is identical with dilution halogenating agent solvent for use.Now, the solvent be advantageously selected from hexane, hexamethylene, pentane, heptane or
Its mixture, is especially hexamethylene.Five block copolymers of polymer based on the solvent of halogenation employing and preparation
Identical solvent, can avoid solvent recovery problem.
Additionally, in the application preparation method, when solvent is using non-polar solven, can avoid because using polar solvent
As the recovery problem brought by halogenated alkane or tetrahydrofuran.
Used as five block base copolymer for treating halogenation, which can be prepared by conventional method.The base polymer is usual
Synthesized using anionic solution polymerization method.Polymerization initiator adopt difunctional alkyl's lithium class initiator, this include two lithium butane,
Divinylbenzene class Dilithium initiator etc..Solvent is usually used nonpolar class alkane, such as hexane, hexamethylene, pentane, heptane,
White oil or its mixture etc., it is also possible to using aromatic hydrocarbon solvent, such as benzene, alkylbenzene etc..In addition, during copolymerization, depending on technological requirement, can
To add structure regulator before polymerization or in polymerization process, structure regulator is generally also monomer reactivity ratio conditioning agent, including
Some ethers and amine substance, such as tetrahydrofuran, ether, 2G, N, N, N ', N '-tetramethylethylenediamine etc..Polymerization is generally in 30-
Carry out at 100 DEG C.Polymerization is finished, and needs to add terminator, such as some alcohols materials, such as methyl alcohol, isopropanol etc., and water can also be straight
Connect as terminator.
In the present invention, add isoprene monomer in a solvent first, bifunctional initiator is subsequently adding, treats isoamyl
Diene completely after completion of the reaction, adds divinylic monomer；Treat that diene monomers add styrene monomer, benzene second completely after completion of the reaction
Alkene monomer after completion of the reaction, adds terminator terminating reaction.
Embodiment
For a more detailed description to the present invention with embodiment below.These embodiments are all only the present invention to be preferable to carry out
The description of scheme, should not be construed as having any restriction to protection scope of the present invention.
In following examples and comparative example, before and after halogenation, the structural characterization of polymer uses Bruker
AVANCE400MHz NMR spectra instrument；
The glass transition temperature of polymer is determined using Pekin-Elmer DMA-7E dynamic visco-elasticity analyser, frequency 1Hz,
Heating rate is 2 DEG C/min；
The peel strength of pressure sensitive adhesive is according to GB-2792-81 standard test；The formula of pressure sensitive adhesive is as follows：Rubber (non-halogenated or
The block copolymer of halogenation)：100 weight portions, hydrogenated petroleum resin：170 weight portions, and naphthenic rubber operation oil：65 weight
Part.
Comparative example 1
In 3L glass kettle, solvent hexamethylene 2000ml and isoprene 36g is added.System is made to heat up using water bath with thermostatic control
Active lithium concentration is added to after 50 DEG C for the two lithium butane Li (CH of 1.0mol/L2)4Li initiator 2.2ml.Keep water bath with thermostatic control 50
DEG C reaction 30min after, add divinylic monomer 84g.After keeping 50 DEG C of reaction 50min of water bath with thermostatic control, styrene monomer is added
80g.After keeping 50 DEG C of water bath with thermostatic control to continue reaction 30min, terminator methyl alcohol 0.1ml is added, obtains polymer solution.By half
Polymer solution proceeds to another 3L glass kettle, adds 0.2g antioxidant 1010 in remaining half polymer solution.Will
Plus non-halogenated polymer product is obtained after the half polymer solution desolvation of antioxidant.The number of products therefrom is divided equally
Son amount is 9.8 × 104, other structures and performance are shown in Table 1.
Embodiment 2
When the half polymer solution temperature proceeded in the 3L glass kettle described in comparative example 1 drops to 30 DEG C, strong
Stirring is lower to add solution of the 22.4g bromine in 400g hexamethylene, and halogenation occurs under the conditions of non-lucifuge.Reaction 5min
Afterwards, it is that the sodium hydrate aqueous solution 250ml of 1.0mol/L and concentration are water-soluble for the sodium pyrosulfite of 1.0mol/L to add concentration
Liquid 50ml, after continuing stirring 10min, adds calcium stearate and each 2.0g of epoxidized soybean oil, and 0.2g antioxidant 1010, is gathered
Polymer solution.Resulting polymers solution deionized water cyclic washing to pH is neutrality, halogenation is obtained after desolvation and is gathered
Compound product.The structure and performance of products therefrom is shown in Table 1.
Comparative example 3
In 3L glass kettle, solvent hexamethylene 2000ml and isoprene monomer 112g is added.Body is made using water bath with thermostatic control
System is warmed up to after 50 DEG C the two lithium butane Li (CH for adding active lithium concentration for 1.0mol/L2)4Li initiator 1.4ml.Keep constant temperature
After 50 DEG C of reaction 30min of water-bath, divinylic monomer 48g is added.After keeping 50 DEG C of reaction 50min of water bath with thermostatic control, styrene is added
Monomer 40g.After keeping 50 DEG C of water bath with thermostatic control to continue reaction 30min, terminator methyl alcohol 0.1ml is added, obtains polymer solution.Will
Half polymer solution proceeds to another 3L glass kettle, adds 0.2g antioxidant in remaining half polymer solution
1010.By plus antioxidant half polymer solution desolvation after obtain non-halogenated polymer product.Products therefrom
Number-average molecular weight be 14.8 × 104, other structures and performance are shown in Table 1.
Embodiment 4
When the half polymer solution temperature proceeded in the 3L glass kettle described in comparative example 3 drops to 30 DEG C, strong
Stirring is lower to add solution of the 5.8g bromine in 40g hexamethylene, and halogenation occurs under the conditions of non-lucifuge.After reaction 5min,
Add the sodium hydrate aqueous solution 250ml that concentration is 1.0mol/L and the metabisulfite solution that concentration is 1.0mol/L
50ml, after continuing stirring 10min, adds calcium stearate and each 2.0g of epoxidized soybean oil, and 0.2g antioxidant 1010, is polymerized
Thing solution.Resulting polymers solution deionized water cyclic washing to pH is neutrality, after desolvation, obtains halogenation polymerization
Produce thing.The structure and performance of products therefrom is shown in Table 1.
Comparative example 5
In 3L glass kettle, solvent hexamethylene 2000ml and isoprene 24g is added.System is made to heat up using water bath with thermostatic control
Active lithium concentration is added to after 50 DEG C for the two lithium butane initiator 2.2ml of 1.0mol/L.Keep 50 DEG C of reactions of water bath with thermostatic control
After 30min, divinylic monomer 116g is added.After keeping 50 DEG C of reaction 50min of water bath with thermostatic control, styrene monomer 60g is added.Keep
After 50 DEG C of water bath with thermostatic control continues reaction 30min, terminator methyl alcohol 0.1ml is added, obtains polymer solution.Will be molten for half polymer
Liquid proceeds to another 3L glass kettle, adds 0.2g antioxidant 1010 in remaining half polymer solution.Antioxidant will be added
Half polymer solution desolvation after obtain non-halogenated polymer product.The number-average molecular weight of products therefrom is
10.2×104, other structures and performance are shown in Table 1.
Embodiment 6
When the half polymer solution temperature proceeded in the 3L glass kettle described in comparative example 5 drops to 30 DEG C, strong
Stirring is lower to add solution of the 28.6g bromine in 100g hexamethylene, carries out halogenation under the conditions of non-lucifuge.Reaction 5min
Afterwards, it is that the sodium hydrate aqueous solution 250ml of 1.0mol/L and concentration are water-soluble for the sodium pyrosulfite of 1.0mol/L to add concentration
Liquid 50ml, after continuing stirring 10min, adds calcium stearate and each 2.0g of epoxidized soybean oil, and 0.2g antioxidant 1010, is gathered
Polymer solution.Resulting polymers solution deionized water cyclic washing to pH is neutrality, halogenation is obtained after desolvation and is gathered
Compound product.The structure and performance of products therefrom is shown in Table 1.
Comparative example 7
In 5L glass kettle, solvent hexamethylene 3000ml and isoprene 54g is added.System is made to heat up using water bath with thermostatic control
Active lithium concentration is added to after 50 DEG C for the two lithium butane Li (CH of 1.0mol/L2)4Li initiator 3.2ml.Keep water bath with thermostatic control 50
DEG C reaction 30min after, add divinylic monomer 126g.After reaction 50min, styrene monomer 120g is added.Keep water bath with thermostatic control
After 50 DEG C are continued reaction 30min, terminator methyl alcohol 0.1ml is added, obtains polymer solution.2/3 polymer solution is proceeded to separately
Two 3L glass kettles are used for halogenation, proceed to 1/3 polymer solution in each kettle, add in remaining 1/3 polymer solution
0.2g antioxidant 1010.By plus antioxidant that 1/3 polymer solution desolvation after obtain non-halogenated polymer product.
The number-average molecular weight of products therefrom is 9.9 × 104, other structures and performance are shown in Table 1.
Embodiment 8
When 1/3 polymer solution temperature of portion proceeded to described in the comparative example 7 drops to 30 DEG C, add under vigorous stirring
, there is halogenation under the conditions of non-lucifuge in solution of the 0.42g bromine in 25g hexamethylene.After reaction 5min, addition concentration is
The sodium hydrate aqueous solution 250ml of 1.0mol/L and concentration are the metabisulfite solution 50ml of 1.0mol/L, continue to stir
After mixing 10min, calcium stearate and each 2.0g of epoxidized soybean oil, and 0.2g antioxidant 1010 is added, obtains polymer solution.By institute
It is neutrality polymer solution deionized water cyclic washing to be obtained to pH, obtains the polymer product of halogenation after desolvation.Institute
Obtain the structure of product and performance is shown in Table 1.
Comparative example 9
When another 1/3 polymer solution temperature proceeded to described in the comparative example 7 drops to 30 DEG C, add under vigorous stirring
, there is halogenation under the conditions of non-lucifuge in solution of the 50.8g bromine in 800g hexamethylene.After reaction 5min, concentration is added
Sodium hydrate aqueous solution 500ml and concentration for 1.0mol/L is the metabisulfite solution 100ml of 1.0mol/L, continues
After stirring 10min, calcium stearate and each 2.0g of epoxidized soybean oil, and 0.2g antioxidant 1010 is added, obtains polymer solution.Will
Resulting polymers solution deionized water cyclic washing is neutrality to pH, obtains the polymer product of halogenation after desolvation.
The structure and performance of products therefrom is shown in Table 1.The polymer has been no longer appropriate for for pressure sensitive adhesive.
The structure of product and performance before and after 1. bromination of table
From in terms of the result of embodiment in table 12,4,6,8, in the case of halogenation degree is suitable, polymer rubber before and after halogenation
The Tg change of glue phase less, illustrates negative effect very little of the halogenation to rubber phase.By contrast, due to the polarity of material after halogenation
Increase, based on halogen polymer, the peel strength of the pressure sensitive adhesive of glue substantially increases.
Comparative example 10
Repeat embodiment 2, difference is：By dilution 22.4g bromine using 400g hexamethylene be kept to 60g hexamethylene
Alkane, bromine diluted concentration are 27.1%.During halogenation, observe that substantial amounts of polymer is wrapped on shaft, it is impossible to separate,
Neutralization and washing.After drying, polymer hardens, and color is changed into red, has been not used to pressure sensitive adhesive.
Claims (44)
1. a kind of segmented copolymer of halogenation, the block copolymer before halogenation be with formula S1-B1-I-B2-S2Structure embedding
Section copolymer, wherein S1And S2It is each independently polystyrene block, B1And B2It is each independently polybutadiene block, and I
For polyisoprene blocks, it is characterised in that in halogenation block copolymer, unsaturated carbon-to-carbon double bond contained by block I
0.4-80% is by halogenation, and B block1And B2Halogenation degree and the unsaturated carbon contained by block I of contained unsaturation carbon-to-carbon double bond-
The ratio of the halogenation degree of carbon double bond is less than 0.01.
2. the segmented copolymer of halogenation according to claim 1, it is characterised in that the halogenation is bromination or chlorination.
3. the segmented copolymer of halogenation according to claim 1, it is characterised in that in halogenation block copolymer, embedding
The 3-75% of the unsaturated carbon-to-carbon double bond contained by section I is by halogenation.
4. the segmented copolymer of halogenation according to claim 3, it is characterised in that in halogenation block copolymer, embedding
The 3-40% of the unsaturated carbon-to-carbon double bond contained by section I is by halogenation.
5. the segmented copolymer of halogenation according to claim 1, wherein in halogenation block copolymer, B block1And B2
The halogenation degree of contained unsaturation carbon-to-carbon double bond is less than with the ratio of the halogenation degree of unsaturated carbon-to-carbon double bond contained by block I
0.005.
6. the segmented copolymer of halogenation according to claim 2, wherein in halogenation block copolymer, B block1And B2
The halogenation degree of contained unsaturation carbon-to-carbon double bond is less than with the ratio of the halogenation degree of unsaturated carbon-to-carbon double bond contained by block I
0.005.
7. the segmented copolymer of halogenation according to claim 3, wherein in halogenation block copolymer, B block1And B2
The halogenation degree of contained unsaturation carbon-to-carbon double bond is less than with the ratio of the halogenation degree of unsaturated carbon-to-carbon double bond contained by block I
0.005.
8. the segmented copolymer of halogenation according to claim 4, wherein in halogenation block copolymer, B block1And B2
The halogenation degree of contained unsaturation carbon-to-carbon double bond is less than with the ratio of the halogenation degree of unsaturated carbon-to-carbon double bond contained by block I
0.005.
9. the segmented copolymer of halogenation according to claim 1, wherein in halogenation block copolymer, B block1And B2
Contained unsaturation carbon-to-carbon double bond is not by halogenation.
10. the segmented copolymer of halogenation according to claim 2, wherein in halogenation block copolymer, B block1And B2
Contained unsaturation carbon-to-carbon double bond is not by halogenation.
The segmented copolymer of 11. halogenations according to claim 3, wherein in halogenation block copolymer, B block1And B2
Contained unsaturation carbon-to-carbon double bond is not by halogenation.
The segmented copolymer of 12. halogenations according to claim 4, wherein in halogenation block copolymer, B block1And B2
Contained unsaturation carbon-to-carbon double bond is not by halogenation.
The segmented copolymer of 13. halogenations according to claim 1, wherein number of the halogenation block copolymer before halogenation are equal
Molecular weight is 5 × 104-50×104.
The segmented copolymer of 14. halogenations according to claim 1, wherein number of the halogenation block copolymer before halogenation are equal
Molecular weight is 5 × 104-30×104.
The segmented copolymer of 15. halogenations according to any one of claim 1-14, the wherein block before halogenation are altogether
In polymers, based on the gross weight of the block copolymer before halogenation, styrenic monomer units content is 10-70 weight %, butadiene
Monomer unit content is 10-80 weight %, and isoprene monomer unit content is 10-80%.
The segmented copolymer of 16. halogenations according to any one of claim 1-14, the wherein block before halogenation are altogether
In polymers, based on the gross weight of the block copolymer before halogenation, styrenic monomer units content is 20-60 weight %, butadiene
Monomer unit content is 10-70 weight %, and isoprene monomer unit content is 10-70 weight %.
The segmented copolymer of 17. halogenations according to any one of claim 1-14, the wherein block before halogenation are altogether
In polymers, based on the gross weight of the block copolymer before halogenation, styrenic monomer units content is 20-40 weight %, butadiene
Monomer unit content is 20-60 weight %, and isoprene monomer unit content is 10-60%.
The segmented copolymer of 18. halogenations according to any one of claim 1-14, wherein S1And S2It is identical polyphenyl
Ethylene block, and/or, B1And B2It is identical polybutadiene block.
The segmented copolymer of 19. halogenations according to claim 15, wherein S1And S2It is identical polystyrene block,
And/or, B1And B2It is identical polybutadiene block.
The segmented copolymer of 20. halogenations according to claim 16, wherein S1And S2It is identical polystyrene block,
And/or, B1And B2It is identical polybutadiene block.
The segmented copolymer of 21. halogenations according to claim 17, wherein S1And S2It is identical polystyrene block,
And/or, B1And B2It is identical polybutadiene block.
A kind of 22. methods of the halogenation segmented copolymer prepared as required by any one of claim 1-21, including making halogen
Formula S before change1-B1-I-B2-S2The solution of the block copolymer of structure is reacted with halogenating agent.
23. methods according to claim 22, wherein prepare formula S before halogenation1-B1-I-B2-S2The block copolymer of structure molten
The solvent that liquid is used is non-polar alkane.
24. methods according to claim 22, wherein prepare formula S before halogenation1-B1-I-B2-S2The block copolymer of structure molten
The solvent that liquid is used is hexane, hexamethylene, pentane, heptane or its mixture.
25. methods according to claim 22, wherein prepare formula S before halogenation1-B1-I-B2-S2The block copolymer of structure molten
The solvent that liquid is used is hexamethylene.
26. methods according to claim 22, the wherein addition of halogenating agent should cause the halogenating agent and formula S1-B1-I-B2-S2Embedding
In section copolymer, contained by all isoprene monomer units, the mol ratio of unsaturated carbon-to-carbon double bond is 0.01-1.0.
27. methods according to claim 26, the wherein addition of halogenating agent should cause the halogenating agent and formula S1-B1-I-B2-S2Embedding
In section copolymer, contained by all isoprene monomer units, the mol ratio of unsaturated carbon-to-carbon double bond is 0.04-0.6.
28. methods according to claim 22, wherein halogenating agent are chlorine or bromine.
29. methods according to claim 24, wherein halogenating agent are chlorine or bromine.
30. methods according to claim 26, wherein halogenating agent are chlorine or bromine.
31. methods according to claim 27, wherein halogenating agent are chlorine or bromine.
Halogenating agent beyond dechlorination is wherein diluted to halogenating agent by 32. methods according to any one of claim 22-31
Content for 0.2-25.0 weight % solution after again with halogenation before formula S1-B1-I-B2-S2The solution of the block copolymer of structure
Reaction.
Halogenating agent beyond dechlorination is wherein diluted to halogenating agent by 33. methods according to any one of claim 22-31
Content for 0.5-15.0 weight % solution after again with halogenation before formula S1-B1-I-B2-S2The solution of the block copolymer of structure
Reaction.
Halogenating agent beyond dechlorination is wherein diluted to halogenating agent by 34. methods according to any one of claim 22-31
Content for 1.0-6.0 weight % solution after again with halogenation before formula S1-B1-I-B2-S2The solution of the block copolymer of structure is anti-
Should.
35. methods according to claim 32, the solvent that wherein dilution halogenating agent is used is non-polar alkane.
36. methods according to claim 32, the solvent that wherein dilution halogenating agent is used is hexane, hexamethylene, pentane, heptan
Alkane or its mixture.
37. methods according to claim 32, the solvent that wherein dilution halogenating agent is used is hexamethylene.
38. methods according to claim 32, solvent and formula S prepared before halogenation that wherein dilution halogenating agent is used1-B1-
I-B2-S2The solvent that the solution of the block copolymer of structure is used is identical.
39. methods according to any one of claim 22-31, wherein first synthesize formula S before halogenation in a solvent1-B1-
I-B2-S2The block copolymer of structure, obtains formula S1-B1-I-B2-S2The solution of block copolymer, is not separating the block copolymerization
Just the solution of gained block copolymer and halogenating agent is reacted in the case of thing.
40. methods according to claim 39, wherein just by gained block in the case of the block copolymer is not separated
The solution of copolymer is reacted with the halogenating agent of dilution.
41. methods according to claim 39, wherein synthesis type S1-B1-I-B2-S2It is molten that the block copolymer of structure is used
Agent is non-polar alkane.
42. methods according to claim 39, wherein synthesis type S1-B1-I-B2-S2It is molten that the block copolymer of structure is used
Agent is hexane, hexamethylene, pentane, heptane or its mixture.
43. methods according to claim 39, wherein synthesis type S1-B1-I-B2-S2It is molten that the block copolymer of structure is used
Agent is hexamethylene.
44. methods according to claim 40, wherein synthesis type S1-B1-I-B2-S2It is molten that the block copolymer of structure is used
Agent is identical with dilution halogenating agent solvent for use.
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