CN103087279B - Thermoplastic elastomer containing polar styrene block and preparation method thereof - Google Patents

Thermoplastic elastomer containing polar styrene block and preparation method thereof Download PDF

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Publication number
CN103087279B
CN103087279B CN201310027910.4A CN201310027910A CN103087279B CN 103087279 B CN103087279 B CN 103087279B CN 201310027910 A CN201310027910 A CN 201310027910A CN 103087279 B CN103087279 B CN 103087279B
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thermoplastic elastomer
preparation method
styrene block
add
characterized
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CN201310027910.4A
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Chinese (zh)
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CN103087279A (en
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赵忠夫
白雪
张春庆
李战胜
胡雁鸣
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大连理工大学
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Abstract

The invention discloses a thermoplastic elastomer containing polar styrene block and a preparation method thereof. The elastomer is characterized by being a polymer which adopts a linear styrene elastomer polymer as a main chain and is connected with a polar branch chain at the styrene block. The preparation method of the elastomer comprises the following steps of: synthesizing the main chain containing a lithiation unit by virtue of an anionic coupling technology; carrying out lithiation reaction on the main chain; and adding the polar monomer and carrying out chain propagation reaction of the ethylene oxide side chain by utilizing generated lithiation points. The polarity of the thermoplastic elastomer is increased by the polar branch chain; and the defect that the bonding effect of an adhesive using SBC (Polyethylene Polypropylene Fiber) as a substrate is non-ideal is solved.

Description

A kind of thermoplastic elastomer that contains polarity styrene block and preparation method thereof

Technical field

The invention belongs to pressure sensitive adhesive field, relate to a kind of thermoplastic elastomer that contains polarity styrene block and preparation method thereof.

Background technology

SBC has unique molecular structure as the important elastomer material of a class, and in the middle of it, diene block provides certain visco-elasticity, and two ends polystyrene (PS) block plays the effect of intermolecular chemical reinforcement or physical crosslinking.At normal temperatures, PS block can form physics cross-linking set, makes to form between molecule reticulated structure, can operative constraint middle element chain, and make SBC there is good caoutchouc elasticity; At high temperature, this constraint will disappear, and makes SBC show good thermoplasticity; Therefore, SBC polymkeric substance is the elastomer material that a class can be carried out melt-processed, has a wide range of applications.

SBC has high solid substances content, quick-drying, low temperature resistant feature when the sizing agent.SBC can be divided into styrene-butadiene-styrene block copolymer (SBS), styrene isoprene styrene block copolymer (SIS) (SIS) and their corresponding hydrogenation products by block composition.Because at present SIS and SBS obtain by the method for anionoid polymerization, be difficult in polymerization process, directly introduce polar molecule, make the adhesion property of they and polar material poor, the application of the pressure sensitive adhesive that to have limited SBC be matrix.

In order to improve the polarity of SBC, scientific research personnel mainly adopts the method for introducing polar functional group and grafting polarity side chain.Utilizing in SBC molecule carbon-carbon double bond to carry out epoxidation reaction is one of more ripe polar-modified method, and the SBC polarity after epoxidation increases, and cohesive strength improves, and can overcome SBC is the sizing agent shortcoming undesirable to polar material bond effect of matrix.But the polar group of introducing by this kind of method makes the reactivity of originally submissive diolefine segment reduce the motion that limits polymer segment, has improved the second-order transition temperature of diene block.Chinese patent CN1528798A provides a kind of maleic anhydride graft SBS solvent process for thermosynthesizing, in autoclave, put into SBS, maleic anhydride, initiator and common monomer, obtain the SBS of grafted maleic anhydride side chain in conjugated diolefine hydrocarbon segment, similarly also had bulk graft modification.These methods will be used a large amount of noxious solvents, can be to environments and by the consumption producing two keys, and the adhesion property of SBC base polymer is reduced, thereby affected the application of this base polymer in sizing agent industry.

The present invention adopts the method for anionoid polymerization to synthesize in a kind of PS block, to contain polarity side chain polystyrene thermoplastic elastomer.In the styrene block of this thermoplastic elastomer, containing can lithiumation unit, in the situation that not affecting middle diene block structure, the active site of introducing anionoid polymerization by lithiation on styrene block, adds polar monomer, has introduced polarity side chain on nonpolar molecular chain.The introducing of polarity side chain increases thermoplastic elastomer polarity, has overcome the shortcoming undesirable to polar material bond effect as the sizing agent of matrix.

Summary of the invention

The present invention seeks to adopt the method for anionoid polymerization, the thermoplastic elastomer that contains polarity side chain in synthetic PS block.

A kind of thermoplastic elastomer that contains polarity styrene block that the present invention is prepared, it is that styrene block has the polymkeric substance of polarity side chain taking line style styrenic thermoplastic elastomer polymkeric substance as main chain, its structural formula is shown in formula (1):

The number-average molecular weight of its main chain is 8 × 10 4~12 × 10 4; End styrene block contains can lithiumation unit, can lithiumation unit and the mol ratio of styrene units be 1/99~30/70; Divinyl or isoprene are middle conjugated diene block, and the mass ratio of end styrene block and middle conjugated diene block is 20/80~40/60; The number-average molecular weight of styrene block Semi-polarity side chain is 5 × 10 2~1 × 10 4; In its styrene block, can there is as shown in the formula the structure shown in (2) lithiumation unit the alkyl of R for containing 1 ~ 4 carbon, allyl group.

The preparation method of the thermoplastic elastomer that contains polarity side chain in above-mentioned PS block, comprises the steps:

Step 1: adopt coupling method to prepare line style styrenic thermoplastic elastomer; First to the mixture solution that adds vinylbenzene/can lithiumation monomer in reactor, then add organic lithium initiator, polyreaction 1~6 hour; Polymerization temperature is 30~70 DEG C; Continue to add conjugated diene monomer to carry out polymerization; Then add coupling agent to carry out linked reaction; The mol ratio of initiator and coupling agent is 1:0.5~1; Linked reaction 1~6 hour, linked reaction temperature is 30~100 DEG C; After condensing, being dried, obtain line style styrenic thermoplastic elastomer;

Step 2: in line style styrenic thermoplastic elastomer polymers soln, add lithiation reagent, lithiumation promotor, carries out lithiation to line style styrenic thermoplastic elastomer; Then be neutral by solution washing to ph, then add this solvent to carry out next step reaction.

Step 3: add polar monomer in the synthetic system generating to step 2, carry out the transfer reaction of side chain.

Being applicable to organic lithium initiator of the present invention can be lithium alkylide, lithium aryl, aralkyl lithium, cycloalkyl lithium, and initiator amount is determined according to the relative molecular mass of polymkeric substance; Coupling agent is ethylene dichloride, ethylene dibromide or ethylidene periodide; The selected solvent of the present invention is the polarity good solvent of polystyrene thermoplastic elastomer, if selected solvent is toluene, ethylbenzene, dimethylbenzene or tetrahydrofuran (THF) etc.; Lithiation reagent is n-Butyl Lithium or s-butyl lithium; The polar monomer adding is oxyethane, methyl methacrylate, methyl acrylate, methylene malonate, α-cyanoacrylate, vinyl cyanide or methacrylonitrile.The all operations of this invention all carries out under protection of inert gas, and rare gas element used is nitrogen, argon gas or helium.

Embodiment

Following examples are only illustrative, the scope not limiting the present invention in any way.

The preparation of the SBS that embodiment 1 contains p-methylstyrene

In polymerization bottle, add the solvent measuring, 4-vinyl toluene/cinnamic the mixture of different proportionings, activator THF, after 40 ~ 50 DEG C of preheating half an hour, add n-butyl lithium initiator according to the design of molecular weight, react 3 hours, add the divinyl measuring, controlling temperature of reaction is 80 DEG C again, continues reaction 1 hour, add coupling agent 1,2-ethylene dibromide, temperature maintains between 75 ~ 100 DEG C, after reacting 1 hour, stopped reaction, products therefrom is for subsequent use after condensing, wash, being dried.Experimental data is listed in table 1, and product structure test result is listed in table 2.Table one

Table two

Embodiment 2 carries out lithiumation and graft reaction to embodiment 1 gained SBS-1

At 50 DEG C, the SBS-1 of 2g is dissolved in 100ml polymerization bottle with 50ml toluene, and to add 5ml concentration be the n-Butyl Lithium of 1.4mol/L and the TMEDA of 2ml, carry out lithiation, react after 2 hours, add toluene repeated washing to be neutral to the ph of washings, import 30ml toluene, add 1g oxirane monomers, carry out end capping, react 10 hours at 40 DEG C, add 0.6mmol phosphonitrile at-50~-40 DEG C afterwards, carry out the graft reaction of side group epoxy ethane, react 3 days at 40 DEG C.Institute responds and all under argon shield, carries out, and obtains taking polyethylene oxide as side chain, SBS is the thermoplastic elastomer polymkeric substance of main chain.Product structure test result is as shown in table 3.

Embodiment 3 carries out lithiumation and graft reaction to embodiment 1 gained SBS-2

At 50 DEG C, the SBS-2 of 2g is dissolved in 100ml polymerization bottle with 50ml tetrahydrofuran (THF), and to add 5ml concentration be the n-Butyl Lithium of 1.4mol/L and the TMEDA of 1ml, carry out lithiation, react after 3 hours, add tetrahydrofuran (THF) repeated washing to the ph of washings for neutral, import 30ml tetrahydrofuran (THF), add 1.5g oxirane monomers, carry out end capping, in the 10 hours reaction times at 40 DEG C, add 0.2mmol phosphonitrile at-50~-40 DEG C afterwards, carry out the graft reaction of side group epoxy ethane, react 3 days at 50 DEG C.Institute responds and all under argon shield, carries out, and obtains taking polyethylene oxide as side chain, SBS is the thermoplastic elastomer polymkeric substance of main chain.Product structure test result is as shown in table 3.

Embodiment 4 carries out lithiumation and graft reaction to embodiment 1 gained SBS-3

At 50 DEG C, the SBS-3 of 2g is dissolved in 100ml polymerization bottle with 50ml toluene, and to add 4ml concentration be the n-Butyl Lithium of 1.4mol/L and the TMEDA of 2ml, carry out lithiation, reaction times is 1 hour, and adding toluene repeated washing is neutrality to ph, importing 30ml toluene, add again 1g oxirane monomers, carry out end capping, react 10 hours at 40 DEG C, add catalyzer 0.56mmol at-50~-40 DEG C afterwards, carry out the graft reaction of side group epoxy ethane, react 3 days at 50 DEG C.Institute responds and all under argon shield, carries out, and obtains taking polyethylene oxide as side chain, SBS is the thermoplastic elastomer polymkeric substance of main chain.Product structure test result is as shown in table 3.

Embodiment 5 carries out lithiumation and graft reaction to embodiment 1 gained SBS-1

At 50 DEG C, the SBS-1 of 2g is dissolved in 100ml polymerization bottle with 50ml toluene, and to add 5ml concentration be the n-Butyl Lithium of 1.4mol/L and the TMEDA of 2ml, carry out lithiation, react after 2 hours, add toluene repeated washing to be neutral to the ph of washings, import 30ml toluene, add 1g methyl methacrylate to carry out the graft reaction of side chain, react 3 hours at-50 DEG C.Institute responds and all under argon shield, carries out, and obtains taking polymethylmethacrylate as side chain, SBS is the thermoplastic elastomer polymkeric substance of main chain.Product structure test result is as shown in table 3.

Table three

Claims (9)

1. a thermoplastic elastomer that contains polarity styrene block, is characterized in that, this thermoplastic elastomer is that styrene block has the polymkeric substance of polarity side chain taking line style styrenic thermoplastic elastomer polymkeric substance as main chain, and its structure is shown in formula (1);
In described styrene block, can its structure of lithiumation unit be shown in formula (2), R be alkyl or the allyl group that contains 1~4 carbon;
2. thermoplastic elastomer according to claim 1, is characterized in that, the number-average molecular weight of described line style styrenic thermoplastic elastomer polymkeric substance is 8 × 10 4~12 × 10 4, styrene block contains can lithiumation unit, can lithiumation unit and the mol ratio of styrene units be 1/99~30/70; Divinyl or isoprene are middle conjugated diene block, and the mass ratio of styrene block and middle conjugated diene block is 20/80~40/60.
3. thermoplastic elastomer according to claim 1, is characterized in that, the number-average molecular weight of styrene block Semi-polarity side chain is 5 × 10 2~1 × 10 4.
4. the preparation method of the arbitrary described thermoplastic elastomer of claim 1~3, its feature comprises the following steps:
Step 1: adopt coupling method to prepare line style styrenic thermoplastic elastomer; First to the solution of mixture that adds vinylbenzene/can lithiumation monomer in reactor, then add organic lithium initiator, polyreaction 1~6 hour; Polymerization temperature is 30~70 DEG C; Continue to add conjugated diene monomer to carry out polymerization; Then add coupling agent to carry out linked reaction; The mol ratio of initiator and coupling agent is 1:0.5~1; Linked reaction 1~6 hour, linked reaction temperature is 30~100 DEG C; After condensing, being dried, obtain line style styrenic thermoplastic elastomer;
Step 2: in line style styrenic thermoplastic elastomer polymers soln, add lithiation reagent, lithiumation promotor, line style styrenic thermoplastic elastomer is carried out to lithiation; Then be neutral by solution washing to ph, then add this solvent to carry out next step reaction;
Step 3: add polar monomer in the synthetic system generating to step 2, carry out the transfer reaction of side chain.
5. preparation method according to claim 4, is characterized in that: the polar monomer adding is oxyethane, methyl methacrylate, methyl acrylate, methylene malonate, α-cyanoacrylate, vinyl cyanide or methacrylonitrile.
6. preparation method according to claim 4, is characterized in that: organic lithium initiator is lithium alkylide, lithium aryl, aralkyl lithium or cycloalkyl lithium; Initiator amount is determined according to the relative molecular mass of polymkeric substance; Described coupling agent is ethylene dichloride, ethylene dibromide or ethylidene periodide.
7. preparation method according to claim 4, is characterized in that: lithiation reagent is n-Butyl Lithium or s-butyl lithium; Lithiumation promotor refers to Tetramethyl Ethylene Diamine or tert.-butoxy potassium.
8. preparation method according to claim 4, is characterized in that: the polarity good solvent that selected solvent is styrene series thermoplastic elastomer.
9. preparation method according to claim 8, is characterized in that: selected solvent is toluene, ethylbenzene, dimethylbenzene or tetrahydrofuran (THF).
CN201310027910.4A 2013-01-24 2013-01-24 Thermoplastic elastomer containing polar styrene block and preparation method thereof CN103087279B (en)

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