CN107337748B - A kind of styrene copolymer and preparation method thereof with reversible crosslink key - Google Patents
A kind of styrene copolymer and preparation method thereof with reversible crosslink key Download PDFInfo
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Abstract
The invention discloses a kind of styrene copolymer and its preparation method and application with reversible crosslink key.The present invention, which is reacted using the styrene copolymer with furyl with polyfunctionality maleimide derivatives, generates reversible crosslink key, improves the solvent resistance of styrene copolymer material.Reversible crosslink key in styrene copolymer material provided by the invention with reversible crosslink key can disconnect at high temperature, and material has suitability for secondary processing, and it can be used repeatedly.
Description
Technical field
The invention belongs to styrene copolymers, and in particular to a kind of styrene copolymer with reversible crosslink key and its
Preparation method and purposes.
Background technique
Styrene copolymer is that there are the polymer materials of polystyrene chain segment, such as polyphenyl second in strand for one kind
Alkene/Butadiene/Styrene block copolymer (SBS), styrene/ethylene-butylene/styrene block copolymer (SEBS), polyphenyl
Ethylene/isoprene/styrene block copolymer (SIS), polystyrene/isoprene/styrene block copolymer (SIS),
Polystyrene/ethylene-propylene/styrene block copolymer (SEPS), polystyrene/Ethylene-Propylene Block Copolymer (SEP)
Deng.There is phase region made of being intertwined as strand soft segment and hard section, soft, hard segment difference under room temperature in these material matrix
In viscous state, glassy state, but high resiliency is presented in hard section limitation soft segment flowing, material；Soft under high temperature, hard segment is in viscosity flow
Thermoplasticity is integrally presented in state, material, this characteristic makes them be commonly used for preparing blending and modifying PP Pipe Compound.Wherein, electric wire electricity
Cable cladding insulating materials, solid tire of bicycle are exactly one of its widest application.
Styrene copolymer as wire cable material, solid tyre, it is necessary to have good solvent resistance.Styrene
Analog copolymer is nonpolar linear macromolecule, and resistance to dissolubility is poor, encounters gasoline, toluene, hexamethylene equal solvent, then quickly dissolution,
Mechanical property sharp fall, is not available.It is well known that molecule interchain linkage is to improve the best side of polymer solvent resistance
Method, the styrene copolymer as wire cable material, solid tyre also need to can be carried out secondary operation in addition to energy solvent resistant.Often
Though rule chemical crosslinking can improve its solvent resistant, the ability for making it lose post forming.
Summary of the invention
The purpose of the present invention is to provide a kind of styrene copolymer with reversible crosslink key and preparation method thereof and use
On the way.
A kind of preparation method of phenylethylene cross-linked copolymer, step are as follows: the styrene copolymer with furyl and more
Degree of functionality maleimide derivatives are made by polymerisation in solution or melt polymerization；
The polymerisation in solution are as follows: the styrene copolymer with furyl is dissolved in preparation concentration in organic solvent and is not surpassed
The copolymer solution for crossing 30wt% adds polymerization inhibitor, polyfunctionality maleimide derivatives, 80~140 DEG C react 6~
For 24 hours, it is settled out product, it is obtained by drying；
The melt polymerization are as follows: polymerization inhibitor, polyfunctionality are sequentially added into the styrene copolymer with furyl
Maleimide derivatives are kneaded 15-120 minutes at 170-240 DEG C, and cooling to obtain the final product；
Wherein, the dosage of the styrene copolymer with furyl and bismaleimide amine derivative is that can make maleimide
The amount that amido reacts completely；
The styrene copolymer with furyl is the preparation method comprises the following steps: hydroxyl styrene copolymer is dissolved
It is single to sequentially add catalyst, the activity containing furyl for the solution that hydroxyl styrene copolymer is obtained into organic solvent
Body, 20~50 DEG C of 2~6h of reaction go out product with water sedimentation after reaction, obtained by drying；
Wherein, the molar ratio of hydroxyl is in the styrene copolymer of the activated monomer and hydroxyl containing furyl
0.5~3:1；
The catalyst is pyridine, pyridine derivate, tertiary amine, carbodiimide derivative, any in organo-tin compound
It is one or more, 0.001~5:1 of mole ratio of catalyst and the activated monomer with furyl；
The hydroxyl styrene copolymer number-average molecular weight is 0.1 ten thousand~500,000.
Further, the styrene copolymer number-average molecular weight M with furylnFor 0.1 ten thousand < Mn< 120 ten thousand；It is preferred that
Ground, the styrene copolymer number-average molecular weight M with furylnFor 50,000≤Mn≤ 85 ten thousand.
Further, the styrene derivative structural unit with furan group accounts for all structural units in copolymer
Mass fraction N is 0 < N≤75%, preferably 5%≤N≤55%.
Further, 2 or 2 or more maleimides are contained in the polyfunctionality maleimide derivatives
Functional group, preferably N, N'- (4,4'- methylenediphenyl) bismaleimide, N, N'- (Isosorbide-5-Nitrae-phenylene) bismaleimide
Amine, 1,2- bis- (maleimide base oxethyl) ethane, N, penylene bismaleimide, 1,2- bis- (maleimide) between N'-
Bis- (dimaleoyl imino) butane of ethane, 1,4-, 1,6- bis- (dimaleoyl imino) hexane.
Further, dimaleoyl imino and the benzene second with furyl in the polyfunctionality maleimide derivatives
The molar ratio of furyl is 0.1~1:1 in vinyl copolymer.
Further, in the solution polymerization process, organic solvent is total for the phenylethylene of energy while dissolving band furyl
The solvent of polymers and polyfunctionality maleimide derivatives, preferably toluene, dimethylbenzene, tetrahydrofuran, methylene chloride, trichlorine
Methane；And/or the mass concentration of the styrene copolymer solution with furyl is 10%~20%.
Further, the polymerization inhibitor is one of phenolic compound, quinones, oxynitrides or more
Kind；And/or the molar ratio of the polymerization inhibitor and polyfunctionality maleimide derivatives is 0~2:100.
Further, hydroxyl structure unit accounts for all structure lists in copolymer in the hydroxyl styrene copolymer
The mass fraction P of member is 0 < P≤33%, preferably 3≤P≤25%；And/or the hydroxyl styrene copolymer
The mass concentration of solution is no more than 30%；And/or the activated monomer with furyl is furoyl chloride, furancarboxylic acid, chaff
Any one in alcohol, chaff amine；And/or hydroxyl in the styrene copolymer of the activated monomer and hydroxyl containing furyl
The molar ratio of base unit is 1~2:1.
A kind of phenylethylene cross-linked copolymer reacts reversible with dimaleoyl imino containing furyl in molecule
Cross-bond, swellbility of the phenylethylene cross-linked copolymer in toluene are 3.8~34.2.
A kind of phenylethylene cross-linked copolymer, it is prepared by above-described preparation method.
A kind of purposes of above-mentioned phenylethylene cross-linked copolymer, can be used for preparing solvent resistant and can post-forming process repeatedly
Wire cable material, tire.
The cross-bond that heretofore described reversible crosslink key refers to that reactant reaction generates can disconnect under certain condition,
The cross-bond is reversible crosslink key.
Styrene copolymer prepared by the present invention with reversible crosslink key overcomes existing linear styrene's macromolecular material
The shortcomings that expecting poor solvent resistance, while overcoming the shortcomings that styrene of existing chemical crosslinking is without capacity to reprocess.The present invention
The existing preferable solvent resistance of the phenylethylene analog copolymer with reversible crosslink key is prepared, and there is secondary operation to form energy
Power.
Obviously, above content according to the present invention is not being departed from according to the ordinary technical knowledge and customary means of this field
Under the premise of the above-mentioned basic fundamental thought of the present invention, the modification, replacement or change of other diversified forms can also be made.
Detailed description of the invention
The styrene copolymer preparation flow figure of Fig. 1 key containing reversible crosslink.
The FTIR spectrum of Fig. 2 hydroxyl styrene copolymer (sample 1-2).
The FTIR spectrum of styrene copolymer (sample 1-2 be made) of the Fig. 3 with furyl.
Fig. 4 hydroxyl styrene copolymer (sample 1-2)1H NMR figure.
Fig. 5 is with furyl styrene copolymer (sample 1-2 is made)1H NMR figure.
The styrene copolymer material (2) of Fig. 6 hydroxyl styrene copolymer (1) and the key containing reversible crosslink it is resistance to
Solvent borne.
The depolymerization of the styrene copolymer material of Fig. 7 key containing reversible crosslink.
Specific embodiment
The specific embodiment of form by the following examples remakes further specifically above content of the invention
It is bright.But the range that this should not be interpreted as to the above-mentioned theme of the present invention is only limitted to example below.It is all to be based on above content of the present invention
The technology realized all belongs to the scope of the present invention.
Reagent used in the embodiment of the present invention mainly has: 4- ethylene benzyl acetic acid esters, to 4- acetoxy-styrene, positive fourth
Base lithium (1.6M), styrene, furfuryl alcohol, methyl diphenylene diisocyanate are purchased in Adamas Reagent Company；Alchlor, two
Chloroethyl aluminium, aluminium diethyl monochloride, furans acyl chlorides, chaff amine are purchased in Aladdin Reagent Company；Tin tetrachloride (1M) purchase in
Acros Reagent Company, toluene di-isocyanate(TDI) are purchased in TCI Reagent Company, are conventional commercial product.
With CDCl3As solvent, obtained copolymer is carried out with Bruker AV 600MHz Nuclear Magnetic Resonance1H NMR
Test.
Using chloroform as solvent, after KBr salt on piece film, using Nieolet NEXUS670 Fourier infrared spectrograph device
Carry out infrared test.
Molecular weight is tested using 1525 type gel permeation chromatograph of Water, and tetrahydrofuran is leacheate (1ml/
Min), standard polystyren is as reference.
Sample is immersed in toluene, is impregnated 24 hours, is wiped the solvent on surface after taking-up rapidly, and weigh, write down weight
ω 2, weight is denoted as ω 3 after vacuum drying, and the initial mass of sample is ω 1, calculates swellbility (SD) according to following formula and coagulates
Glue content (GD):
Using 5567 type universal material test machine of INSTRON according to the stretching of ASTM D-638-08 testing standard test specimens
Intensity, tensile speed 50mm/min.
Embodiment 1
(1) anionic polymerisation prepares hydroxyl styrene-ethylene/butylene-styrene linear block copolymers
1L polymeric kettle is vacuumized, three times with high pure nitrogen displacement, the hexamethylene of 650ml purifying is first added, design contains admittedly
Amount 10%.Match and feed by Tables 1 and 2, be first added first segment to 4- ethylene benzyl acetic acid esters and styrene mix monomer,
0.25ml tetrahydrofuran, opens stirring, then n-butyllithium solution (concentration 0.5M) is added by table 2, reacts 1 hour at 40 DEG C, then
Butadiene is added, the reaction was continued 1 hour, the 4- ethylene benzyl acetic acid esters and styrene mix monomer of third section are finally added,
It reacts again 1 hour.After reaction, it by polymeric liquid indentation plus hydrogen kettle, is passed through hydrogen and terminates reaction.After half an hour, 1mL is added
Concentration is 0.02mol/L o-methyl benzoic acid methyl ester, 30mg catalyst cyclopentadienyl titanium dichloride, then be passed through hydrogen, control temperature 70 C,
Pressure 2MPa, reaction discharge after terminating 6 hours.
The mol ratio of mix monomer in 1 embodiment 1 of table
As shown in Figure 1, addition 10ml concentration is 50wt% sodium hydroxide aqueous alkali, buck into (1) product mixture
Tetrabutylammonium bromide containing 5wt% in solution hydrolyzes 3 hours in 60 DEG C, methanol is finally added into reaction solution, precipitates product,
And it dries to get hydroxyl styrene-ethylene/butylene-styrene block copolymer is arrived.Its synthesizing formula and technique and point
Son measures test result and is shown in Table 2, and infrared spectroscopy is shown in Fig. 2,1H NMR is shown in Fig. 4.
The synthesizing formula of the hydroxyl styrene-ethylene/butylene-styrene linear block copolymers of table 2
(2) styrene-ethylene/butylene-styrene block copolymer containing furyl is prepared
5g hydroxy styrenes-ethylene/butylene-styrene block copolymer is dissolved in chloroform, mass concentration 10% is obtained
Solution, furans acyl chlorides is added by formula shown in table 3,4-dimethylaminopyridine (DAMP) is slowly added to pyridine, and dosage is furans
1.5 times of acyl chlorides mole, after room temperature reaction 6 hours, ethyl alcohol, which is added, is precipitated out product, and filtration drying is to get containing furans
The styrene-ethylene/butylene-styrene block copolymer of base, infrared spectroscopy are shown in Fig. 3,1H NMR test result is shown in Fig. 5.
(3) the styrene-ethylene/butylene-styrene block copolymer material of the key containing reversible crosslink is prepared
N, N'- (4,4'- methylene is added to the styrene-ethylene/butylene-styrene block copolymer of gained furyl
Diphenyl) bismaleimide, 0.003mmol 2- tert-butyl hydroquinone is 15 small in 100 DEG C of reactions in xylene solvent
When, solvent is sloughed, solvent-proof styrene-ethylene/butylene-styrene block copolymer, performance such as table 3 are obtained.
The synthesizing formula and property of the styrene-ethylene/butylene-styrene block copolymer material of 3 key containing reversible crosslink of table
Energy
It can be seen from the above result that the present invention uses styrene copolymer and N containing furyl, N'- (4,4'- methylene
Diphenyl) bismaleimide crosslinking preparation crosslinked styrene copolymers improve the resistance to molten of polystyrene copolymer well
Agent performance, wherein sample 1-1,1-2 crosslinking after solvent resistance it is especially good, can be used for wire and cable cladding insulating materials, from
Solid tyre of driving a vehicle etc..
Embodiment 2
(1) anionic polymerisation prepares the star-like styrene-ethylene/butylene-styrene block copolymer of hydroxyl
By the formula of 1-4,1-5,1-6 and 1-7 in table 1, the linear benzene of the acetic acid esters of ethylene benzyl containing 4- structural unit is synthesized
Material is pressed by ethylene-butadiene-styrene linear block copolymers after third section reaction monomers are added and react 1 hour
Add hydrogen kettle, be formulated by table 4, coupling agent is added, 40 DEG C of the reaction was continued 30min obtain the acetic acid esters structural unit of ethylene benzyl containing 4-
Star-like Styrene-Butadiene-Styrene Block Copolymer glue.
Hydrogenation treatment according to the method for embodiment 1 after reaction, is settled out product and dries, obtain 4- ethylene benzyl second
The star-like styrene-ethylene/butylene-styrene block copolymer glue of acrylate structure unit.
Product is dissolved in normal octane and forms solution, addition 50ml concentration is 40wt% sodium hydroxide aqueous alkali, is contained
5wt% cetyl trimethylammonium bromide hydrolyzes 1 hour in 70 DEG C, then it is 10% hydrogen that reaction solution, which is slowly injected into 100 DEG C of concentration,
Glue is boiled in sodium oxide molybdena boiling water, removes solvent and other impurities, is settled out product, is dried to get hydroxylated star-like styrene-is arrived
Ethylene/butylene-styrene block copolymer.
The synthesizing formula and molecule measuring of the star-like styrene-ethylene/butylene-styrene block copolymer of 4 hydroxyl of table
Examination
(2) the star-like styrene-ethylene/butylene-styrene block copolymer containing furyl is synthesized
The hydroxylated star-like styrene-ethylene/butylene-styrene block copolymer of 5g is dissolved in chloroform to obtain quality dense
2- furancarboxylic acid, 4-dimethylaminopyridine (DAMP), two Asia of dicyclohexyl carbon is added by formula shown in table 5 in the solution of degree 10%
Amine (DCC), after 80 DEG C are reacted 6 hours, ethyl alcohol, which is added, is precipitated out product, and filtration drying is to get the star-like benzene containing furyl
Ethylene-vinyl/butylene-styrene block copolymer.
The synthesizing formula of the star-like styrene-ethylene/butylene-styrene block copolymer material of 5 key containing reversible crosslink of table
And performance
(3) the star-like styrene-ethylene/butylene-styrene block copolymer material of the key containing reversible crosslink is prepared
N, N'- (1,4- are added into star-like styrene-ethylene/butylene-styrene block copolymer of the gained containing furyl
Phenylene) bismaleimide, 0.004mmol methylnaphthohydroquinone obtains solvent-proof star-like benzene second in 170 DEG C of mill 120min
Alkene-ethylene/butylene-styrene block copolymer material.
Embodiment 3
(1) anionic polymerisation prepares hydroxyl styrene-ethylene/propylene-styrene block copolymer
1L polymeric kettle is vacuumized, three times with high pure nitrogen displacement, the hexamethylene of 650ml purifying is first added, design contains admittedly
Amount 15%, then by table 6 and the formula charging of table 7.First segment is first added to 4- acetoxy-styrene and styrene mix monomer, 1g
Tetrahydrofurfuryl alcohol ethylether opens stirring, adds tert .-butyllithium solution (concentration 0.5M), reacts 50min at 60 DEG C, then heats to
70 DEG C plus isoprene, the reaction was continued 1 hour, finally adds third section and mixes list to 4- acetoxy-styrene and styrene
Body, then react 1 hour.After reaction, it by polymeric liquid indentation plus hydrogen kettle, is passed through hydrogen and terminates reaction.After half an hour, 30mg
Catalyst (nickel naphthenate/triisobutyl aluminium, n (A) l:n (Ni)=5:1), then it is passed through hydrogen, control temperature 50 C, pressure
0.5MPa discharges after reaction, precipitates, filtering.
The mol ratio of mix monomer in 6 embodiment 2 of table
Product is dissolved in normal heptane or n-hexane, addition 50ml concentration is 30wt% sodium hydroxide aqueous alkali, in buck
Tetrabutylammonium bromide containing 15wt% hydrolyzes 3 hours in 60 DEG C, methanol is finally added into reaction solution, precipitates product, and dries
It does to get hydroxyl styrene-ethylene/propylene-styrene block copolymer is arrived.Its synthesizing formula and technique and molecular weight
Test result is shown in Table 7.
The hydroxyl styrene-ethylene of table 7/propylene-styrene block copolymer synthesizing formula and molecular weight test knot
Fruit
(2) styrene-ethylene containing furyl/propylene-styrene block copolymer is prepared
Under stiring, furancarbinol is slowly dropped in toluene di-isocyanate(TDI), controls furancarbinol and isocyanates
Dosage is 1.1:1, and dibutyl tin dilaurate is added by the 0.1% of furancarbinol mole dosage, and 50 DEG C are reacted 2 hours, are obtained
End group is the furans of isocyanate group.It again will be containing 5g hydroxyl styrene-ethylene/propylene-styrene block copolymer four
Hydrogen tetrahydrofuran solution (mass concentration 30%) is added drop-wise in the furans that end group is isocyanate group that (end group is the furans of isocyanate group
8) dosage is shown in Table, the reaction was continued at 50 DEG C 2 hours, and distilled water is added, is precipitated out product, and filtration drying is to get to containing furan
It mutters styrene-ethylene/propylene-styrene block copolymer of base.
(3) styrene-ethylene/propylene-styrene block copolymer material of the key containing reversible crosslink is prepared
Bis- (the maleimides of 1,2- are added to styrene-ethylene/propylene-styrene block copolymer of gained furyl
Base oxethyl) ethane, 0.002mmol tetramethyl piperidine nitrogen oxides, in toluene solvant in 100 DEG C react 15 hours, be added
Methanol extraction is simultaneously dried, and styrene-ethylene/propylene-styrene block copolymer material of the solvent-proof key containing reversible crosslink is obtained
Material, performance such as table 8.
The synthesizing formula and property of the styrene-ethylene/butylene-styrene block copolymer material of 8 key containing reversible crosslink of table
Energy
It can be seen from the above result that the present invention passes through the styrene copolymer with furyl and 1, the bis- (maleimides of 2-
Base oxethyl) ethane crosslinking preparation crosslinked styrene copolymers swellbility it is lower, improve polystyrene copolymer well
Solvent resistance.
Embodiment 4
(1) anionic polymerisation prepares hydroxyl styrene-α-methylstyrene-butadiene random copolymer
100ml chloroform, 0.1mol 4- ethenylphenyl methanol, 0.1mol cyclopenta formyl are added into 500ml flask
Chlorine, 0.6g 4-dimethylaminopyridine, 8g pyridine react 12 hours at 20 DEG C.Distilled water is added after reaction, wait be layered, takes
Organic layer is washed with distilled water 5 times repeatedly, is evaporated under reduced pressure at last 50 DEG C, is removed chloroform and water, is obtained to 4- ethylene benzyl ring
Pentylformic acid ester.
1L polymeric kettle is vacuumized, three times with high pure nitrogen displacement, the hexamethylene of 650ml purifying is first added, design contains admittedly
Amount 10%.It sequentially adds to 11.6g 4- ethylene benzyl cyclopenta formic acid esters (accounting for monomer molar content 7.1%), 4.17g benzene second
Alkene, 1.2g α-methylstyrene, 0.59mol butadiene, 0.234mmol N, N- dimethyl tetrahydro chaff amine, open stirring, add
2.08ml Sec-Butyllithium solution (concentration 0.5M) reacts at 60 DEG C 2 hours, is finally pressed into reaction solution and terminates in kettle, second is added
Alcohol terminates reaction.
Into product mixture, addition 15ml concentration is 40wt% sodium hydroxide aqueous alkali, contains 5wt% 12 in buck
Alkyl trimethyl ammonium bromide hydrolyzes 2 hours in 80 DEG C, methanol is finally added into reaction solution, precipitates product, and dries, i.e.,
Obtain hydroxyl styrene-α-methylstyrene-butadiene random copolymer, number-average molecular weight about 4.8 ten thousand, molecular weight distribution
Width 1.17, the structural unit accounting example 15.4wt% of hydroxyl.
(2) styrene-α-methylstyrene-butadiene random copolymer containing furyl is prepared
Chaff amine is slowly dropped in methyl diphenylene diisocyanate, two laurels are added by the 0.5% of chaff amine mole
Sour dibutyl tin, controls chaff amine and isocyanates dosage is 1.05:1, and 40 DEG C are reacted 2 hours, and terminal isocyanate group furans is obtained
3.1g.By styrene-α-methylstyrene-butadiene random copolymer tetrahydrofuran solution of the hydroxyl containing 5g, (quality is dense again
20%) degree is added drop-wise in terminal isocyanate group furans, 50 DEG C are reacted 2 hours, and distilled water is added, is precipitated out product, is filtered
It dries to get the styrene butadiene random copolymer containing furyl is arrived.
(3) styrene-α-methylstyrene-butadiene random copolymer material of the key containing reversible crosslink is prepared
4.95mmol N, N'- is added to styrene-α-methylstyrene-butadiene random copolymer of gained furyl
Between penylene bismaleimide, 0.005mmol tetramethyl piperidine nitrogen oxides reacts 10 hours in 120 DEG C of toluene, obtains resistance to molten
The styrene-α-methylstyrene of agent-butadiene random copolymerization material, swellbility 4.5, gel content 81%, tensile strength
22.3MPa。
Embodiment 5 (1) anionic polymerisation process prepares hydroxyl styrene-isoprene random copolymer
The addition 100ml chloroform into 500ml flask, 6.71g 4- ethenylphenyl methanol, 8.43g 3- phenylpropionyl chloride,
0.6g 4-dimethylaminopyridine, 9g triethylamine react 9 hours at 25 DEG C.Distilled water is added after reaction, wait be layered, has taken
Organic layer is washed with distilled water 5 times repeatedly, is evaporated under reduced pressure at last 50 DEG C, is removed chloroform and water, is obtained to 4- ethylene benzyl (3-
Phenyl) propionic ester.
1L polymeric kettle is vacuumized, three times with high pure nitrogen displacement, the hexamethylene of 650ml purifying is first added, design contains admittedly
Amount 10%.It sequentially adds to 13.31g to 4- ethylene benzyl (3- phenyl) propionic ester (accounting for monomer molar content 9.0%), 5.2g benzene
Ethylene, 31g isoprene, 0.30mmol dimethylformamide, open stirring, add 1.66ml n-butyllithium solution (concentration
0.5M), it reacts at 40 DEG C 3 hours, finally reaction solution is pressed into and is terminated in kettle, ethyl alcohol is added and terminates reaction.
Into product mixture, addition 15ml concentration is 36wt% sodium hydroxide aqueous alkali, benzyl containing 8wt% in buck
Triethylammonium bromide hydrolyzes 10 hours in 45 DEG C, methanol is finally added into reaction solution, precipitates product, and dries to get arriving
Hydroxyl styrene-isoprene random copolymer, number-average molecular weight about 5.9 ten thousand, molecular weight distribution width 1.12, hydroxyl
Structural unit accounting example 15.64wt%.
(2) the styrene-isoprene random copolymer containing furyl is prepared
The styrene-isoprene random copolymer of 5g hydroxyl is dissolved in dichloroethanes, mass concentration 15% is controlled, adds
Enter 14.5mmol furans acyl chlorides, 1mmol 4-dimethylaminopyridine (DAMP) is slowly added to 0.09mol pyridine, and room temperature reaction 8 is small
Shi Hou, ethyl alcohol, which is added, is precipitated out product, and filtration drying is to get the styrene-isoprene random copolymer containing furyl.
(3) the styrene-isoprene random copolymer material of the key containing reversible crosslink is prepared
5mmol N is added to the styrene-isoprene random copolymer of gained furyl, penylene span carrys out acyl between N'-
Imines, 0.01mmol tetramethyl piperidine nitrogen oxides react 10 hours in 120 DEG C of toluene, and methanol extraction is added and dries, obtains
Solvent-proof styrene-isoprene random copolymer, swellbility 3.8, gel content 78%, tensile strength 24.3MPa.
Embodiment 6
(1) cationic polymerization process prepares hydroxyl styreneisobutylene random copolymer
Solid content 8% is controlled, 500g monochloro methane (being cooled to -60 DEG C in advance), 7.81g benzene second are sequentially added into 1L polymeric kettle
Alkene, 4.4g are opened and are uniformly mixed to 4- ethylene benzyl acetic acid esters (accounting for monomer molar content 4.2%), 27.8g isobutene, and
It is cooled to -80 DEG C or so.Start the hexane solution that 20ml ethyl aluminum dichloride containing 12.8mmol/L is slowly added dropwise into reaction kettle,
And maintain polymerization temperature.The reaction was continued after being added dropwise to complete 15 minutes, and what then addition 2ml was precooled contains 0.125mol/L hydrogen-oxygen
The ethanol solution for changing sodium terminates polymerization, removes reaction dissolvent and washes, dries, obtains the acetic acid esters structural unit of ethylene benzyl containing 4-
Styreneisobutylene random copolymer.
Product is dissolved in 1L toluene, addition 30ml concentration is 45wt% potassium hydroxide aqueous alkali, contains 5wt% in buck
Tetrabutylammonium chloride hydrolyzes 8 hours in 50 DEG C, methanol is finally added into reaction solution, makes product precipitating, washing, and dry, i.e.,
Obtain hydroxyl styreneisobutylene random copolymer, molecular weight 16.2 ten thousand, molecular weight distribution width 5.6, the knot of hydroxyl
Structure unit accounting example 8.6wt%.
(2) the styreneisobutylene random copolymer containing furyl is prepared
The styreneisobutylene random copolymer of 5g hydroxyl is dissolved in chloroform, synthesis contains furans as described in Example 5
The styreneisobutylene random copolymer of base, furoyl chloride dosage are 9mmol, and DAMP dosage is constant, is slowly added to
0.045mol pyridine.
(3) the styreneisobutylene random copolymer material of the key containing reversible crosslink is prepared
3.6mmol N is added to the styreneisobutylene random copolymer of gained furyl, penylene span carrys out acyl between N'-
Imines, 0.002mmol methylnaphthohydroquinone react 10 hours in 120 DEG C of toluene, and methanol extraction is added and dries, obtains solvent resistant
Styreneisobutylene random copolymer, swellbility 6.9, gel content 68%, tensile strength 21.3MPa.
Embodiment 7
(1) cationic polymerization process prepares hydroxyl styrene-isoprene random copolymer
Controlling solid content is 8%, according to the method for 6 step 1 of embodiment, reaction dissolvent be n-hexane, 7.81g styrene,
To 4- ethylene benzyl acetic acid esters (accounting for monomer molar content 4.2%), 27.8g isoprene, reaction temperature is -30 DEG C, draws 4.4g
The dichloromethane solution that agent is 5.5ml 50mmol/L titanium tetrachloride is sent out, the reaction time 45 minutes, other conditions were identical, then water
Solution, obtains hydroxyl styrene-isoprene random copolymer, molecular weight 15.9 ten thousand, and molecular weight distribution width 6.2 contains hydroxyl
The structural unit accounting example 8.6wt% of base.
(2) the styreneisobutylene random copolymer containing furyl is prepared
The styrene-isoprene random copolymer of 5g hydroxyl is dissolved in hexamethylene, synthesis contains as described in Example 5
The styrene-isoprene random copolymer of furyl, furoyl chloride mole dosage are 9mmol, and DAMP dosage is constant, slowly
0.045mol pyridine is added.
(3) the styrene-isoprene random copolymer material of the key containing reversible crosslink is prepared
Bis- (maleimide of 1.62mmol 1,2- is added to the styrene-isoprene random copolymer of gained 5g furyl
Amine) ethane, 0.001mmol methylnaphthohydroquinone, in 140 DEG C haloform reaction 6 hours, it is cooling that simultaneously ethanol precipitation is added, filter and dries,
Obtain solvent-proof styrene-isoprene random copolymer, swellbility 24.1, gel content 52.2%, tensile strength
12.6MPa。
Embodiment 8
(1) cationic polymerization process prepares hydroxyl styreneisobutylene -3-methyl-1-butene random copolymer
Solid content 10% is controlled, 500g monochloro methane (being cooled to -80 DEG C in advance), 15g are sequentially added into 1L polymeric kettle to 4-
Ethylene benzyl acetic acid esters (accounting for monomer molar content 12%), the isobutene that 35g molar ratio is 20:1/3 methyl-1s-butylene mixing
Object is opened and is uniformly mixed, and is cooled to -100 DEG C or so.Start to be slowly added dropwise 11ml into reaction kettle containing 19.5mmol/L tri-
The dichloromethane solution of aluminium chloride, and maintain polymerization temperature.The reaction was continued after being added dropwise to complete 12 minutes, and 3ml pre-cooling is then added
The methanol solution containing 0.125mol/L sodium hydroxide crossed terminates polymerization, removes reaction dissolvent and washes, dries, obtains containing 4-
Ethylene benzyl acetic acid esters-isobutene -3-methyl-1-butene random copolymer.
Product is dissolved in 1L dimethylbenzene, addition 40ml concentration is 25wt% potassium hydroxide aqueous alkali, is contained in buck
5wt% tetradecyltrimethylammonium bromide hydrolyzes 12 hours in 35 DEG C, methanol is finally added into reaction solution, precipitate product,
Washing, and dry to get arrive hydroxyl styreneisobutylene -3-methyl-1-butene random copolymer, molecular weight 26.6 ten thousand,
Molecular weight distribution width 4.5, the structural unit accounting example 24wt% of hydroxyl.
(2) styreneisobutylene containing furyl -3-methyl-1-butene random copolymer is prepared
5g hydroxyl styreneisobutylene -3-methyl-1-butene random copolymer is dissolved in chloroform, by embodiment 2
The method of sample 2-1 synthesizes the styreneisobutylene containing furyl -3-methyl-1-butene random copolymer, furancarboxylic acid mole
Dosage is 22mmol, DMAP with DCC dosage is identical.
(3) styreneisobutylene -3-methyl-1-butene random copolymer material of the key containing reversible crosslink is prepared
5.6mmol 1,6- bis- is added to styreneisobutylene -3-methyl-1-butene random copolymer of gained furyl
(dimaleoyl imino) hexane, 0.003mmol 2- tert-butyl hydroquinone, the back flow reaction 23 hours in 80 DEG C of methylene chloride,
It is warming up to 140 DEG C again to react 1 hour, methanol extraction is added and dries, obtains solvent-proof styreneisobutylene-3- methyl-1-
Butene random copolymer, swellbility 4.1, gel content 78%, tensile strength 15.3MPa.
Embodiment 9
(1) cationic polymerization process prepares hydroxyl styreneisobutylene -4-methyl-1-pentene random copolymer
Solid content 15% is controlled, 500g methylene chloride (being cooled to -90 DEG C in advance), 8.1g are sequentially added into 1L polymeric kettle to 4-
Acetoxy-styrene (accounting for monomer molar content 4.3%), 6.9g styrene, 60g molar ratio are 15:1 isobutene/4- methyl-
1- pentene mixture, opens and is uniformly mixed, and is cooled to -110 DEG C or so.Start 30ml is slowly added dropwise into reaction kettle and contain
The hexane solution of 21.3mmol/L aluminium diethyl monochloride, and maintain polymerization temperature.The reaction was continued after being added dropwise to complete 20 minutes, so
The precooled methanol solution containing 0.2mol/L potassium hydroxide of 3ml is added afterwards and terminates polymerization, removes reaction dissolvent and washes, does
It is dry, it obtains containing the styreneisobutylene to 4- acetoxy-styrene structural unit -4-methyl-1-pentene random copolymer.
Product is dissolved in 1L hexamethylene, addition 30ml concentration is 30wt% sodium hydroxide aqueous alkali, is contained in buck
5wt% tricaprylmethyl ammonium bromide hydrolyzes 9 hours in 45 DEG C, ethyl alcohol is finally added into reaction solution, makes product precipitating, washing,
And it dries to get hydroxyl styreneisobutylene -4-methyl-1-pentene random copolymer, molecular weight 11.8 ten thousand, molecule is arrived
Measure the dispersion of distribution 4.3, the ratio 8.2wt% of the structural unit of hydroxyl.
(2) styreneisobutylene containing furyl -4-methyl-1-pentene random copolymer is synthesized
5g hydroxyl styreneisobutylene -4-methyl-1-pentene random copolymer is dissolved in tetrahydrofuran, by real
It is randomly total to apply the used method of sample 3-5 and styreneisobutylene -4-methyl-1-pentene of the formula synthesis containing furyl in example 3
Polymers.(3) styreneisobutylene -4-methyl-1-pentene random copolymer material of the key containing reversible crosslink is prepared
It is bis- that 2.1mmol 1,2- is added to styreneisobutylene -4-methyl-1-pentene random copolymer of gained furyl
(maleimide base oxethyl) ethane, 0.001mmol 2,5- di-tert-butyl hydroquinone are anti-in 80 DEG C of tetrahydrofuran reflux
It answers 22 hours, then is warming up to 120 DEG C and reacts 2 hours, methanol extraction is added and dries, obtain solvent-proof styreneisobutylene
Random copolymer, swellbility 5.2, gel content 64.2%, tensile strength 16.7MPa.
Embodiment 10
(1) cationic polymerization process prepares hydroxyl styreneisobutylene -1,3- pentadiene random copolymer
Solid content 15% is controlled, 500g dichloroethanes (being cooled to -20 DEG C in advance), 9.8g are sequentially added into 1L polymeric kettle to 4-
Acetoxy-styrene (accounting for monomer molar content 4.3%), 5.2g styrene, 60g molar ratio are 15:1 isobutene/1,3- penta 2
Alkene mixture, opens and is uniformly mixed.The methylene chloride that 18.75ml tin tetrachloride containing 20mmol/L is injected into reaction kettle is molten
Liquid, and maintain polymerization temperature the reaction was continued 1 hour, the precooled methanol containing 0.2mol/L potassium hydroxide of 3ml is then added
Solution terminates polymerization, removes reaction dissolvent and washes, dries, obtains containing the benzene second to 4- acetoxy-styrene structural unit
Alkene-isobutene -1,3- pentadiene random copolymer.
Product is dissolved in 1L hexamethylene, addition 20ml concentration is 50wt% sodium hydroxide aqueous alkali, is contained in buck
5wt% tetrabutylammonium bromide hydrolyzes 12 hours in 30 DEG C, reaction solution is poured into boiling water, product is settled out, and obtains after drying
Hydroxyl styreneisobutylene -1,3-pentadiene random copolymer, molecular weight 29.2 ten thousand, molecular weight distribution width 3.8 contain
The ratio 10.02wt% of the structural unit of hydroxyl.
(2) styreneisobutylene -1,3- pentadiene random copolymer containing furyl is synthesized
5g hydroxyl styreneisobutylene -1,3-pentadiene random copolymer is dissolved in methylene chloride, by embodiment
Styreneisobutylene -1,3- pentadiene the random copolymer of the used method of sample 3-4 and formula synthesis containing furyl in 3.
(3) styreneisobutylene -1,3- pentadiene random copolymer material of the key containing reversible crosslink is prepared
Bis- (the Malaysias 21mmol 1,4- are added to the styreneisobutylene -1,3- pentadiene random copolymer of 40g furyl
Imide) butane, 0.42mmol p methoxy phenol, in 240 DEG C mixing 15 minutes, obtain solvent-proof styrene-isobutyl
Olefinic random copolymer, swellbility 15.2, gel content 58.9%, tensile strength 14.5MPa.
The present invention carries out the styrene copolymer material of the resulting key containing reversible crosslink of sample 1-2 in embodiment 1
Solvent resistance (Fig. 6) and disaggregation test (Fig. 7).Hydroxyl styrene copolymer (sample 1-2) at normal temperature, dissolves quickly
In toluene, as shown in Fig. 6 (1).Furyl styrene copolymer and N, N'- (4,4'- methylenediphenyl) span carry out acyl
Imines reacts the styrene copolymer material for generating the key containing reversible crosslink at 100 DEG C, and resulting materials are placed in toluene solution
In, after placing for 24 hours under room temperature, material cannot be still dissolved in toluene, as shown in Fig. 6 (2) and the lower-left Fig. 7 figure, show furyl
Styrene copolymer be crosslinked, show good solvent resistance；After heating 4h at 140 DEG C, material can be complete
Fully dissolved (Fig. 7 bottom-right graph) in toluene illustrates at high temperature, reversible crosslink key is broken, and has re-formed band furans
The styrene copolymer and maleimide of base, thus can be carried out and process again.
The present invention is reacted using the styrene copolymer containing furyl with maleimide derivatives, and the benzene of crosslinking is generated
Ethene copolymer improves the solvent resistance of styrene copolymer.As shown in fig. 7, at high temperature, cross-bond can disconnect
It goes to be crosslinked, product has capacity to reprocess.In conclusion the styrene copolymer solvent resistance of crosslinking prepared by the present invention
It is good, and there is suitability for secondary processing.
Claims (15)
1. a kind of preparation method of phenylethylene cross-linked copolymer, it is characterised in that: the styrene copolymer with furyl with
Polyfunctionality maleimide derivatives are made by polymerisation in solution or melt polymerization；
The polymerisation in solution are as follows: the styrene copolymer with furyl is dissolved in preparation concentration in organic solvent and is no more than
The copolymer solution of 30wt% adds polymerization inhibitor, polyfunctionality maleimide derivatives, 80~140 DEG C react 6~
For 24 hours, it is settled out product, it is obtained by drying；
The melt polymerization are as follows: polymerization inhibitor, polyfunctionality Malaysia are sequentially added into the styrene copolymer with furyl
Imide derivative is kneaded 15-120 minutes at 170-240 DEG C, and cooling to obtain the final product；
Wherein, the dosage of the styrene copolymer with furyl and maleimide derivatives is that dimaleoyl imino can be kept complete
The amount of full response；
The styrene copolymer with furyl is the preparation method comprises the following steps: hydroxyl styrene copolymer has been dissolved into
The solution that hydroxyl styrene copolymer is obtained in solvent, sequentially adds catalyst, the activated monomer containing furyl, and 20
~50 DEG C of 2~6h of reaction produce object with water and/or alcohol precipitating after reaction, obtained by drying；
Wherein, the activated monomer containing furyl is any one in the furan derivatives that can directly or indirectly react with hydroxyl
Kind；Activated monomer containing the furyl and molar ratio of hydroxyl is 0.5~3:1 in the styrene copolymer of hydroxyl；
The catalyst is pyridine, pyridine derivate, tertiary amine, carbodiimide derivative, any one in organo-tin compound
Or a variety of, 0.001~5:1 of mole ratio of catalyst and the activated monomer with furyl；
The hydroxyl styrene copolymer number-average molecular weight is 0.1 ten thousand~500,000.
2. preparation method according to claim 1, it is characterised in that: hydroxyl in the hydroxyl styrene copolymer
The mass fraction P that structural unit accounts for all structural units in copolymer is 0 < P≤33%；And/or the hydroxyl styrene
The mass concentration of the solution of analog copolymer is no more than 30%；And/or the activated monomer with furyl be furoyl chloride,
Furancarboxylic acid, furfuryl alcohol, any one in chaff amine；And/or the phenylethylene of the activated monomer and hydroxyl containing furyl
The molar ratio of hydroxy unit is 1~2:1 in copolymer.
3. preparation method according to claim 2, it is characterised in that: hydroxyl in the hydroxyl styrene copolymer
The mass fraction P that structural unit accounts for all structural units in copolymer is 3≤P≤25%.
4. preparation method according to claim 1, it is characterised in that: the styrene copolymer number with furyl is equal
Molecular weight MnFor 0.1 ten thousand < Mn< 120 ten thousand.
5. the preparation method according to claim 4, it is characterised in that: the styrene copolymer number with furyl is equal
Molecular weight MnFor 50,000≤Mn≤ 85 ten thousand.
6. preparation method according to claim 1, it is characterised in that: the styrene derivative structure list with furyl
The mass fraction N that member accounts for all structural units in copolymer is 0 < N≤75%.
7. preparation method according to claim 6, it is characterised in that: the styrene derivative structure list with furyl
The mass fraction N that member accounts for all structural units in copolymer is 5%≤N≤55%.
8. preparation method according to claim 1, it is characterised in that: in the polyfunctionality maleimide derivatives
Contain 2 or 2 or more maleimide functionalities.
9. preparation method according to claim 8, it is characterised in that: in the polyfunctionality maleimide derivatives
For N, N'- (4,4'- methylenediphenyl) bismaleimide, N, N'- (1,4- phenylene) bismaleimide, 1,2- are bis-
(maleimide base oxethyl) ethane, N, penylene bismaleimide, 1,2- bis- (maleimide) ethane, 1,4- between N'-
Bis- (dimaleoyl imino) butane, 1,6- bis- (dimaleoyl imino) hexane.
10. preparation method according to claim 1, it is characterised in that: the polyfunctionality maleimide derivatives
The molar ratio of furyl is 0.1~1:1 in middle dimaleoyl imino and the styrene copolymer with furyl.
11. preparation method according to claim 1, it is characterised in that: in the solution polymerization process, organic solvent is energy
The styrene copolymer of dissolving band furyl and the solvent of polyfunctionality maleimide derivatives simultaneously.
12. preparation method according to claim 11, it is characterised in that: the organic solvent is toluene, dimethylbenzene, tetrahydro
Furans, methylene chloride, chloroform；And/or the mass concentration of the styrene copolymer solution with furyl is
10%~20%.
13. preparation method according to claim 1, it is characterised in that: the polymerization inhibitor is phenolic compound, quinones
Close one of object, oxynitrides or a variety of；And/or the polymerization inhibitor and polyfunctionality maleimide derivatives rub
You are than being 0~2:100.
14. a kind of be prepared phenylethylene cross-linked copolymer, feature with any one of claim 1~13 preparation method
It is: the reversible crosslink key obtained in molecule containing furyl and dimaleoyl imino Diene-addition, phenylethylene copolymerzation with cross-linking
Swellbility of the object in toluene is 3.8~34.2.
15. the purposes of phenylethylene cross-linked copolymer described in a kind of claim 14, it is characterised in that: can be used for preparing solvent resistant
And can processing and forming repeatedly wire cable material, tire.
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| CN102803416A (en) * | 2009-06-11 | 2012-11-28 | 汉高公司 | Thermally reversible hot melt adhesive composition containing multifunctional diene and dienophile compounds |
| CN104193852A (en) * | 2014-08-28 | 2014-12-10 | 上海交通大学 | Modified unsaturated rubber and preparation and use methods thereof |
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| CN1898338A (en) * | 2003-12-24 | 2007-01-17 | 陶氏环球技术公司 | Thermoinversion crosslink of polymer |
| CN102803416A (en) * | 2009-06-11 | 2012-11-28 | 汉高公司 | Thermally reversible hot melt adhesive composition containing multifunctional diene and dienophile compounds |
| CN104193852A (en) * | 2014-08-28 | 2014-12-10 | 上海交通大学 | Modified unsaturated rubber and preparation and use methods thereof |
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