CN105199292A - High-performance TPE (thermal plastic elastomers) rail transit gasket and preparation method thereof - Google Patents
High-performance TPE (thermal plastic elastomers) rail transit gasket and preparation method thereof Download PDFInfo
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- CN105199292A CN105199292A CN201510632975.0A CN201510632975A CN105199292A CN 105199292 A CN105199292 A CN 105199292A CN 201510632975 A CN201510632975 A CN 201510632975A CN 105199292 A CN105199292 A CN 105199292A
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Abstract
The invention discloses a high-performance TPE (thermal plastic elastomers) rail transit gasket. The high-performance TPE rail transit gasket is prepared from the following raw materials: maleic anhydride modified SEBS, PP, sulfonated polyimide-siloxane copolymer, amino-terminated polybenzimidazole prepolymer, titanium dioxide and viscosity modifiers. The invention also discloses a preparation method of the high-performance TPE rail transit gasket.
Description
Technical field
The invention belongs to technical field of polymer materials, more specifically, the present invention relates to a kind of high-performance TPE track traffic pad and preparation method thereof.
Background technology
The impact that each wheel bearing passing track vehicle as the railroad tie pad bearing cushioning effect between rail and sleeper produces when moving on tie plate and sleeper and extrusion load.Existing tie plate many by rubber, EVA (ethylene-vinyl acetate copolymer, a kind of hot melt adhesive) or TPU (a kind of adhesion type TPU(Thermoplastic polyurethanes)) make rubber have good elasticity, damping performance but its work-ing life lower; Though and engineering plastics have higher-strength but itself snappiness and dynamic properties cause its damping effect poor.Along with the fast development of modern railway transportation, original rubber pad, EVA pad, TPU pad is caused to be difficult to meet higher damping requirement to pursuit at a high speed.
Thermoplastic elastomer TPE(ThermoplasticElastomer) be a kind of snappiness, high strength, high resilience with rubber, having again can the material of injection molding feature.Have environment-protecting asepsis safety, durometer level is wide, has excellent tint permanence, soft-touch, weathering resistance, fatigue resistance and temperature tolerance, processing characteristics is superior, need not sulfuration, can recycle and reduce costs, both can secondary injection molding, with body material coating and bondings such as PP, PE, PC, PS, ABS, also can be shaping separately, be therefore the ideal material of track traffic pad.But the thermotolerance of TPE is not as rubber, and thus the scope of application is restricted.Meanwhile, compression set, elastic recovery, that weather resistance is equal to rubber phase is poor, still needs further raising.
Therefore, be starved of by formula and the improvement of production technique, can the high-performance TPE track traffic pad of practical requirement to obtain.
Summary of the invention
In order to solve the problem, one aspect of the present invention provides a kind of high-performance TPE track traffic pad, is prepared from by the raw material comprising following weight part:
Maleic anhydride modified SEBS100
PP20～50
Sulfonated polyimide-silicone copolymers 10 ~ 30
Amino-terminated polybenzimidazole prepolymer 5 ~ 10
Titanium dioxide 0.1 ~ 10
Viscosity modifier 1 ~ 40.
In one embodiment, in described maleic anhydride modified SEBS, the percentage of grafting of maleic anhydride is 1 ~ 3%.
In one embodiment, described sulfonated polyimide-silicone copolymers is by amino-terminated sulfonated polyimide prepolymer and silicone-containing dianhydride 1:(0.8 ~ 1.2 in molar ratio) prepare.
In one embodiment, described amino-terminated sulfonated polyimide prepolymer is 1:(0.8 ~ 0.98 by sulfonated diamine and dianhydride in molar ratio) prepare.
In one embodiment, described amino-terminated polybenzimidazole prepolymer is 1:(0.8 ~ 0.98 by tetramine and diacid in molar ratio) prepare.
In one embodiment, described viscosity modifier is at least one in EVA, PVC, LDPE, LLDPE, mLLDPE or ABS.
Another aspect of the present invention provides a kind of preparation method of high-performance TPE track traffic pad, comprises the following steps:
(1) by after the feed composition mixing described in any one of claim 1 ~ 9, through double-screw extruding pelletizing;
(2) by the product of step (1) gained, in 170 DEG C ~ 200 DEG C vacuum injections in mould, keep this temperature after 0.5 ~ 20 hour, then cooling curing obtain.
Be easier to understand the above-mentioned of the application and other features, aspect and advantage with reference to following detailed description.
Embodiment
The detailed description of the following preferred implementation method of the present invention of participation in the election and the embodiment comprised more easily can understand present disclosure.Can mention a large amount of term in following specification sheets and claims, these terms are defined as following implication.
Singulative comprises plural number and object is discussed, unless clearly indicated in addition in context.
" optional " or " optionally " refers to that the item that describes thereafter or event can occur or not occur, and this description comprises situation that event occurs and the situation that event does not occur.
Approximate term in specification sheets and claims is used for modifying quantity, represents that the present invention is not limited to this concrete quantity, also comprises close to this quantity acceptable and can not cause the part of the correction of the change of relevant basic function.Accordingly, modify a numerical value with " approximately ", " about " etc., mean and the invention is not restricted to this exact numerical.In some example, approximate term may correspond to the precision of the instrument measuring numerical value.In present specification and claims, scope limits and can combine and/or exchange, if do not illustrate that these scopes comprise contained all subranges therebetween in addition.
Term as used herein " by ... preparation " and " comprising " synonym.Term used herein " comprises ", " comprising ", " having ", " containing " or its other distortion any, be intended to cover the comprising of non-exclusionism.Such as, comprise the composition of listed elements, step, method, goods or device and need not be only limitted to those key elements, but other key element of clearly not listing or the intrinsic key element of this kind of composition, step, method, goods or device can be comprised.
Conjunction " by ... composition " get rid of any key element, step or the component do not pointed out.If in claim, this phrase will make claim be closed, make it not comprise material except those materials described, but except relative customary impurities.When phrase " by ... composition " to appear in the clause of claim main body instead of immediately preceding after theme time, it is only limited to the key element described in this clause; Other key element is not excluded outside described claim as a whole.
During the Range Representation that equivalent, concentration or other value or parameter limit with scope, preferable range or a series of upper limit preferred value and lower preferable values, this is appreciated that all scopes specifically disclosing and formed by arbitrary pairing of any range limit or preferred value and any range lower limit or preferred value, no matter and whether this scope separately discloses.Such as, when disclosing scope " 1 to 5 ", described scope should be interpreted as comprising scope " 1 to 4 ", " 1 to 3 ", " 1-2 ", " 1-2 and 4-5 ", " 1-3 and 5 " etc.When numerical range is described in this article, unless otherwise indicated, otherwise this scope intention comprises its end value and all integers within the scope of this and mark.
In addition, the indefinite article " one " before key element of the present invention or component and " one " are to quantitative requirement (i.e. occurrence number) unrestriction of key element or component.Therefore " one " or " one " should be read as and comprise one or at least one, and the key element of singulative or component also comprise plural form, unless the obvious purport of described quantity refers to singulative.
One aspect of the present invention provides a kind of high-performance TPE track traffic pad, is prepared from by the raw material comprising following weight part:
Maleic anhydride modified SEBS100
PP20～50
Sulfonated polyimide-silicone copolymers 10 ~ 30
Amino-terminated polybenzimidazole prepolymer 5 ~ 10
Titanium dioxide 0.1 ~ 10
Viscosity modifier 1 ~ 40.
The term " SEBS " used in the application refers to polystyrene to be end segment, the ethylene-butene copolymer obtained with polyhutadiene hydrogenation is the linear three block copolymer of middle spring block, for the application SEBS and have no special requirements, can be commercially available, also can be obtained by synthesis.
Maleic anhydride modified SEBS(MAH-g-SEBS in the application) solution graft copolymerization and fusion-grafting two kinds of methods can be adopted, wherein, when solution grafting carries out SEBS grafting MAH, the graft reaction time is long, and grafting efficiency is low, need to consume poisonous, flammable solvent in a large number, production cost is high, large to human injury, contaminate environment, take up an area large, be difficult to realize continuous operation.Therefore, preferably melt grafting is adopted.
In one embodiment, in described MAH-g-SEBS, the percentage of grafting of MAH is 1% ~ 3%; Preferably, in described MAH-g-SEBS, the percentage of grafting of MAH is 2%.
Polypropylene (PP) in the application is not particularly limited, and can be commercially available or experiment synthesis.
Term " sulfonated polyimide-silicone copolymers " in the application refers to the product obtained by sulfonated polyimide prepolymer and silicone-containing prepolymer.
In one embodiment, described sulfonated polyimide-silicone copolymers is by amino-terminated sulfonation polyamides
Imines prepolymer and silicone-containing dianhydride 1:(0.8 ~ 1.2 in molar ratio) prepare; Preferably, the mol ratio of amino-terminated sulfonated polyimide prepolymer and silicone-containing dianhydride is 1:(0.9 ~ 0.98); More preferably, the mol ratio of amino-terminated sulfonated polyimide prepolymer and silicone-containing dianhydride is 1:0.95.
In one embodiment, described amino-terminated polyimide preformed polymer is 1:(0.8 ~ 0.98 by sulfonated diamine and dianhydride in molar ratio) prepare; Preferably, the mol ratio of sulfonated diamine and dianhydride is 1:0.95.
Described sulfonated polyimide-silicone copolymers can be prepared especially by following method:
(1) preparation of amino-terminated sulfonated polyimide prepolymer
The sulfonated diamine of 1 mole, appropriate meta-cresol and triethylamine is added in the there-necked flask of complete drying, stir under protection of inert gas, after sulfonated diamine dissolves completely, add the dianhydride of 0.8 ~ 0.98 mole and the catalyzer of 2.0 ~ 4.0 moles, at room temperature after stir about 30min, be heated to about 75 ~ 85 DEG C, reaction about 3.5 ~ 4.5h, again at about 175 ~ 185 DEG C, reaction about 3.5 ~ 4.5h; After reaction terminates, be down to room temperature, solution poured in methyl alcohol, has Precipitation; After filtering after removing solvent with methyl alcohol repetitive scrubbing, in vacuum drying oven, dry about 22 ~ 24h at about 50 DEG C, obtain amino-terminated polyimide preformed polymer;
(2) preparation of sulfonated polyimide-silicone copolymers
The above-mentioned amino-terminated polyimide preformed polymer of 1 mole and appropriate meta-cresol is added in the there-necked flask of complete drying, stir under protection of inert gas, after amino-terminated polyimide preformed polymer dissolves completely, add the silicone-containing dianhydride of 0.8 ~ 1.2 mole and the catalyzer of 2.0 ~ 4.0 moles, at room temperature after stir about 30min, be heated to about 75 ~ 85 DEG C, reaction about 3.5 ~ 4.5h, again at about 175 ~ 185 DEG C, reaction about 3.5 ~ 4.5h; After reaction terminates, be down to room temperature, solution poured in methyl alcohol, has Precipitation; Remove after solvent with methyl alcohol repetitive scrubbing and filter, after then using the hydrochloric acid proton exchange 24h of 1mol/L, in vacuum drying oven, dry about 22 ~ 24h at about 50 DEG C with deionized water repetitive scrubbing 3 times, obtain sulfonated polyimide-silicone copolymers.
In one embodiment, described sulfonated diamine is selected from 4,4'-diamino-diphenyl-2,2'-disulfonic acid, 4,4'-
Diamino-3,3'-dimethyl diphenyl methane-2,2'-disulfonic acid, 4,4'-diamino-2,2', 3,3'-dimethyl diphenyl methane-2,2'-disulfonic acid, 4,4'-diamino-2,2'-dimethyl diphenyl-2,2'-disulfonic acid, 4,4'-diamino-3,3'-dimethyl diphenyl-2,2'-disulfonic acid, 4,4'-benzidine-3,3'-disulfonic acid, 2,6'-diaminostilbene, 3,5-tri-methyl p-toluenesulfonate, 3,5-diamino benzene sulfonic acid, 4,4'-diaminodiphenyl oxide-2,2'-disulfonic acid, 3,4'-diaminodiphenyl oxide-2,3'-disulfonic acid, 4,4'-diaminostilbene ' ', 3'' bis-phenoxy group benzene-5''-sulfonic acid, 3,3'-diaminostilbene ' ', 3''-bis-phenoxy group benzene-5''-sulfonic acid, two (4-aminophenyl) fluorenes-2, the 7'-disulfonic acid of 9,9'-, 4,4'-diamino-4'', 4'''-bis-aminophenoxy biphenyl-3'', 3'''-disulfonic acid, 4,4'-diamino-4'', 4'''-bis-phenoxy groups-phenylbenzene isopropyl alkane-5'', 5'''-disulfonic acid or 4,4'-diaminostilbene ' ', 4''-bis-phenoxy groups-benzene-2''-sulfonic acid, 2,2 '-bis-(4-sulfonic group phenoxy group) biphenyl sulfonated diamine, in 3,3 '-bis-(4-sulfonic group phenoxy group) biphenyl sulfonated diamine any one or multiple, preferably, described sulfonated diamine is side chain type, and is selected from 9, two (4-aminophenyl) fluorenes-2 of 9'-, 7'-disulfonic acid, 2, in 2 '-bis-(phenoxy group) biphenyl sulfonated diamine, 3,3 '-bis-(phenoxy group) biphenyl sulfonated diamine any one, more preferably, described sulfonated diamine is 3,3 '-bis-(phenoxy group) biphenyl sulfonated diamine.
In one embodiment, described dianhydride is selected from pyromellitic dianhydride, 3, and 4,9,10-perylene tetracarboxylic acid acid anhydride, 4,4'-(hexafluoro isopropyl alkene) two anhydride phthalic acids, the pungent-7-alkene-2 of dicyclo [2.2.2], 3,5,6-tetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, Isosorbide-5-Nitrae, in 5,8-naphthalenetetracarbacidic acidic dianhydride any one or multiple; Preferably, described dianhydride is selected from 3,4,9,10-perylene tetracarboxylic acid acid anhydride and Isosorbide-5-Nitrae, a kind of in 5,8-naphthalenetetracarbacidic acidic dianhydride or both combinations; More preferably, described dianhydride is Isosorbide-5-Nitrae, 5,8-naphthalenetetracarbacidic acidic dianhydride.
In one embodiment, described silicone-containing dianhydride is selected from 1,3-bis-(3,4-dicarboxyphenyi)-1,1,3,3-
Tetramethyl disiloxane dianhydride, end two (3,4-dicarboxyphenyi) polydimethyl sily oxide dianhydrides and end two (1-norbornane-3,4 dicarboxylic anhydride) polydimethylsiloxane in any one or multiple.
Sulfonated polyimide-silicone copolymers and TPE system have good consistency, and meanwhile, it can also improve the intensity of track traffic pad, wear resistance and shock resistance significantly, because herein is provided Advantageous Effects of the present invention.
Term of the present invention " amino-terminated polybenzimidazole prepolymer " is by excessive tetramine and diacid reactant
Obtain.In one embodiment, described amino-terminated polybenzimidazole prepolymer is 1:(0.8 ~ 0.98 by tetramine and diacid in molar ratio) prepare.Described amino-terminated polybenzimidazole prepolymer can adopt following synthetic method:
Weigh the polyphosphoric acid of certain mass in three-necked flask, connect gas inlet, drying tube, pneumatic outlet and mechanical stirrer, pass into rare gas element, the tetramine of 1 mole is added after 3-5min, the ratio of described polyphosphoric acid and tetramine is 180g/10mmol, when tetramine equably dispersing and dissolving in polyphosphoric acid after, add the diacid of 0.8 ~ 0.98 mole, add Vanadium Pentoxide in FLAKES afterwards to strengthen the absorption to reaction product water, start to stir simultaneously and heat up, be warming up to 200 DEG C, react 20h at such a temperature; After question response system temperature is cooled to 150 DEG C, pour in deionized water, repetitive scrubbing removes polyphosphoric acid; Afterwards product being poured into massfraction is stir 24h in the aqueous sodium hydroxide solution of 7%-10%, afterwards with deionized water repetitive scrubbing removing sodium hydroxide, by amino-terminated for products therefrom polybenzimidazole prepolymer dry for standby at 60 DEG C in vacuum drying oven.
In one embodiment, described tetramine be selected from 3,3'-diaminobenzidine, 3,3', 4,4'-tetramino phenyl ether,
In 3,3', 4,4'-tetramino sulfobenzide, 3,3', 4,4'-tetramino benzophenone, 1,2,4,5-tetramino benzene, 1,2,5,6-tetramino naphthalene any one or multiple in any one or multiple; Preferably, described tetramine is selected from 3,3'-diaminobenzidine, 1,2,4,5-tetramino benzene and 3,3', in 4,4'-tetramino benzophenone any one or multiple; More preferably, described tetramine is 3,3'-diaminobenzidine.
In one embodiment, described diacid is selected oneself diacid, pentanedioic acid, pimelic acid, sebacic acid, 12
In docosandioic acid, terephthalic acid, m-phthalic acid, 2,2'-biphenyl dicarboxylic acids and 4,4'-biphenyl dicarboxylic acid any one or multiple; Preferably, described diacid be selected from pimelic acid, sebacic acid and dodecanedioic acid any one or multiple; More preferably, described diacid is dodecanedioic acid.
Preferably, above-mentioned amino-terminated polybenzimidazole prepolymer pulverizer is pulverized and uses with the particle diameter of 1 ~ 50 μm.
Amino-terminated polybenzimidazole prepolymer can use as oxidation inhibitor on the one hand, can also use as linking agent on the other hand, thus make track traffic pad possess certain crosslinking structure, thus improve its intensity, in addition the resistance of oxidation of imidazole group excellence can also improve the weathering resistance of track traffic pad, because herein is provided Advantageous Effects of the present invention.
Titanium dioxide in the application is not particularly limited, and can be commercially available or experiment synthesis.Titanium dioxide adds as filler, both makes tinting material, has again reinforcement, anti-aging, filling effect.Add titanium dioxide, under sun exposure, sun-resistant, do not ftracture, nondiscoloration, the large and acid-proof alkaline of percentage of elongation improves.
Viscosity modifier for the application is at least one in EVA, PVC, LDPE, LLDPE, mLLDPE or ABS, for improving melt strength.
Another aspect of the present invention provides a kind of preparation method of high-performance TPE track traffic pad, comprises the following steps:
(1) after above-mentioned feed composition being mixed, through double-screw extruding pelletizing;
(2) by the product of step (1) gained, in 170 DEG C ~ 200 DEG C vacuum injections in mould, keep this temperature after 0.5 ~ 20 hour, then cooling curing obtain.
In one preferably embodiment, the temperature of described vacuum injection is 190 DEG C.
Below by embodiment, the present invention is specifically described.What be necessary to herein means out is; following examples are only for the invention will be further described; limiting the scope of the invention can not be interpreted as; some nonessential improvement and adjustment that the professional and technical personnel in this field makes according to the content of the invention described above, still belong to protection scope of the present invention.
In addition, if do not have other to illustrate, raw materials used is all commercially available, and following material number used is weight part.
Raw material:
A1:MAH-g-SEBS(MAH percentage of grafting 1%)
A2:MAH-g-SEBS(MAH percentage of grafting 2%)
A3:MAH-g-SEBS(MAH percentage of grafting 3%)
B1：PP
C1: sulfonated polyimide-silicone copolymers, is prepared by following method:
(1) preparation of amino-terminated sulfonated polyimide prepolymer
1 mole 4 are added in the there-necked flask of complete drying, 4'-diamino-diphenyl-2,2'-disulfonic acid, the meta-cresol of 20 moles and the triethylamine of 2.2 moles, after sulfonated diamine dissolves completely, add the pyromellitic dianhydride of 0.8 mole and the phenylformic acid of 4.0 moles, at room temperature after stir about 30min, be heated to about 80 DEG C, react about 3.5h, then at about 185 DEG C, react about 3.5h; After reaction terminates, be down to room temperature, solution poured in methyl alcohol, has Precipitation; After filtering after removing solvent with methyl alcohol repetitive scrubbing, in vacuum drying oven, dry about 22 ~ 24h at about 50 DEG C, obtain amino-terminated polyimide preformed polymer;
(2) preparation of sulfonated polyimide-silicone copolymers
The above-mentioned amino-terminated polyimide preformed polymer and 20 of 1 mole is added in the there-necked flask of complete drying
Mole meta-cresol, stir under protection of inert gas, after amino-terminated polyimide preformed polymer dissolves completely, add 1,3-bis-(3, the 4-dicarboxyphenyi)-1 of 0.8 mole, 1, the phenylformic acid of 3,3-tetramethyl disiloxane dianhydride and 2.0 moles, at room temperature after stir about 30min, be heated to about 75 DEG C, react about 4.5h, then at about 185 DEG C, react about 24h; After reaction terminates, be down to room temperature, solution poured in methyl alcohol, has Precipitation; Remove after solvent with methyl alcohol repetitive scrubbing and filter, after then using the hydrochloric acid proton exchange 24h of 1mol/L, in vacuum drying oven, dry about 24h at about 50 DEG C with deionized water repetitive scrubbing 3 times, obtain sulfonated polyimide-silicone copolymers.
C2: sulfonated polyimide-silicone copolymers, is prepared by following method:
(1) preparation of amino-terminated sulfonated polyimide prepolymer
1 mole 9 are added in the there-necked flask of complete drying, two (4-aminophenyl) fluorenes-2 of 9'-, 7'-disulfonic acid, the meta-cresol of 20 moles and the triethylamine of 2.2 moles, after sulfonated diamine dissolves completely, add the pyromellitic dianhydride of 0.9 mole and the phenylformic acid of 4.0 moles, at room temperature after stir about 30min, be heated to about 80 DEG C, react about 3.5h, then at about 185 DEG C, react about 3.5h; After reaction terminates, be down to room temperature, solution poured in methyl alcohol, has Precipitation; After filtering after removing solvent with methyl alcohol repetitive scrubbing, in vacuum drying oven, dry about 22 ~ 24h at about 50 DEG C, obtain amino-terminated polyimide preformed polymer;
(2) preparation of sulfonated polyimide-silicone copolymers
The above-mentioned amino-terminated polyimide preformed polymer and 20 of 1 mole is added in the there-necked flask of complete drying
Mole meta-cresol, stir under protection of inert gas, after amino-terminated polyimide preformed polymer dissolves completely, add end two (3,4-dicarboxyphenyi) the polydimethyl sily oxide dianhydride of 1.2 moles and the phenylformic acid of 2.0 moles, at room temperature after stir about 30min, be heated to about 75 DEG C, react about 4.5h, then at about 185 DEG C, react about 24h; After reaction terminates, be down to room temperature, solution poured in methyl alcohol, has Precipitation; Remove after solvent with methyl alcohol repetitive scrubbing and filter, after then using the hydrochloric acid proton exchange 24h of 1mol/L, in vacuum drying oven, dry about 24h at about 50 DEG C with deionized water repetitive scrubbing 3 times, obtain sulfonated polyimide-silicone copolymers.
C3: sulfonated polyimide-silicone copolymers, is prepared by following method:
(1) preparation of amino-terminated sulfonated polyimide prepolymer
1 mole 2 are added in the there-necked flask of complete drying, 2 '-bis-(4-sulfonic group phenoxy group) biphenyl sulfonated diamine, the meta-cresol of 20 moles and the triethylamine of 2.2 moles, after sulfonated diamine dissolves completely, add 0.98 mole 3,4, the phenylformic acid of 9,10-perylene tetracarboxylic acid acid anhydride and 4.0 moles, at room temperature after stir about 30min, be heated to about 80 DEG C, react about 3.5h, then at about 185 DEG C, react about 3.5h; After reaction terminates, be down to room temperature, solution poured in methyl alcohol, has Precipitation; After filtering after removing solvent with methyl alcohol repetitive scrubbing, in vacuum drying oven, dry about 22 ~ 24h at about 50 DEG C, obtain amino-terminated polyimide preformed polymer;
(2) preparation of sulfonated polyimide-silicone copolymers
The above-mentioned amino-terminated polyimide preformed polymer and 20 of 1 mole is added in the there-necked flask of complete drying
Mole meta-cresol, stir under protection of inert gas, after amino-terminated polyimide preformed polymer dissolves completely, add end two (1-norbornane-3, the 4 dicarboxylic anhydride) polydimethylsiloxane of 1 mole and the phenylformic acid of 2.0 moles, at room temperature after stir about 30min, be heated to about 75 DEG C, react about 4.5h, then at about 185 DEG C, react about 24h; After reaction terminates, be down to room temperature, solution poured in methyl alcohol, has Precipitation; Remove after solvent with methyl alcohol repetitive scrubbing and filter, after then using the hydrochloric acid proton exchange 24h of 1mol/L, in vacuum drying oven, dry about 24h at about 50 DEG C with deionized water repetitive scrubbing 3 times, obtain sulfonated polyimide-silicone copolymers.
C4: sulfonated polyimide-silicone copolymers, is prepared by following method:
(1) preparation of amino-terminated sulfonated polyimide prepolymer
1 mole 3 are added in the there-necked flask of complete drying, 3 '-bis-(phenoxy group) biphenyl sulfonated diamine, the meta-cresol of 20 moles and the triethylamine of 2.2 moles, after sulfonated diamine dissolves completely, add 0.95 mole 1,4, the phenylformic acid of 5,8-naphthalenetetracarbacidic acidic dianhydride and 4.0 moles, at room temperature after stir about 30min, be heated to about 80 DEG C, react about 3.5h, then at about 185 DEG C, react about 3.5h; After reaction terminates, be down to room temperature, solution poured in methyl alcohol, has Precipitation; After filtering after removing solvent with methyl alcohol repetitive scrubbing, in vacuum drying oven, dry about 22 ~ 24h at about 50 DEG C, obtain amino-terminated polyimide preformed polymer;
(2) preparation of sulfonated polyimide-silicone copolymers
The above-mentioned amino-terminated polyimide preformed polymer and 20 of 1 mole is added in the there-necked flask of complete drying
Mole meta-cresol, stir under protection of inert gas, after amino-terminated polyimide preformed polymer dissolves completely, add end two (1-norbornane-3, the 4 dicarboxylic anhydride) polydimethylsiloxane of 0.95 mole and the phenylformic acid of 2.0 moles, at room temperature after stir about 30min, be heated to about 75 DEG C, react about 4.5h, then at about 185 DEG C, react about 24h; After reaction terminates, be down to room temperature, solution poured in methyl alcohol, has Precipitation; Remove after solvent with methyl alcohol repetitive scrubbing and filter, after then using the hydrochloric acid proton exchange 24h of 1mol/L, in vacuum drying oven, dry about 24h at about 50 DEG C with deionized water repetitive scrubbing 3 times, obtain sulfonated polyimide-silicone copolymers
D1: amino-terminated polybenzimidazole prepolymer (prepared by 3,3', 4,4'-tetramino phenyl ether and terephthalic acid in molar ratio 1:0.8)
D2: amino-terminated polybenzimidazole prepolymer (prepared by 3,3', 4,4'-tetramino benzophenone and pimelic acid in molar ratio 1:0.98)
D3: amino-terminated polybenzimidazole prepolymer (prepared by 1,2,4,5-tetramino benzene and pimelic acid in molar ratio 1:0.95)
D4: amino-terminated polybenzimidazole prepolymer (prepared by 3,3'-diaminobenzidine and dodecanedioic acid in molar ratio 1:0.95)
E1: titanium dioxide
F1: viscosity modifier EVA
Embodiment 1
After the F1 of the D1 of the C1 of the B1 of the A1 of 100 weight parts, 20 weight parts, 10 weight parts, 5 weight parts, the E1 of 0.1 weight part and 1 weight part is mixed, through double-screw extruding pelletizing;
By the product of above-mentioned gained, in 190 DEG C of vacuum injections in mould, keep this temperature after 5 hours, then cooling curing obtain.
Embodiment 2
After the F1 of the D2 of the C2 of the B1 of the A2 of 100 weight parts, 50 weight parts, 30 weight parts, 10 weight parts, the E1 of 10 weight parts and 40 weight parts is mixed, through double-screw extruding pelletizing;
By the product of above-mentioned gained, in 190 DEG C of vacuum injections in mould, keep this temperature after 5 hours, then cooling curing obtain.
Embodiment 3
After the F1 of the D2 of the C2 of the B1 of the A3 of 100 weight parts, 50 weight parts, 30 weight parts, 10 weight parts, the E1 of 10 weight parts and 40 weight parts is mixed, through double-screw extruding pelletizing;
By the product of above-mentioned gained, in 190 DEG C of vacuum injections in mould, keep this temperature after 5 hours, then cooling curing obtain.
Embodiment 4
After the F1 of the D3 of the C3 of the B1 of the A2 of 100 weight parts, 30 weight parts, 20 weight parts, 8 weight parts, the E1 of 8 weight parts and 15 weight parts is mixed, through double-screw extruding pelletizing;
By the product of above-mentioned gained, in 190 DEG C of vacuum injections in mould, keep this temperature after 5 hours, then cooling curing obtain.
Embodiment 5
After the F1 of the D4 of the C4 of the B1 of the A2 of 100 weight parts, 30 weight parts, 20 weight parts, 8 weight parts, the E1 of 8 weight parts and 15 weight parts is mixed, through double-screw extruding pelletizing;
By the product of above-mentioned gained, in 190 DEG C of vacuum injections in mould, keep this temperature after 5 hours, then cooling curing obtain.
Embodiment 6
After the F1 of the D4 of the C4 of the B1 of the A2 of 100 weight parts, 40 weight parts, 20 weight parts, 8 weight parts, the E1 of 8 weight parts and 20 weight parts is mixed, through double-screw extruding pelletizing;
By the product of above-mentioned gained, in 190 DEG C of vacuum injections in mould, keep this temperature after 5 hours, then cooling curing obtain.
Embodiment 7
After the F1 of the D4 of the C4 of the B1 of the A2 of 100 weight parts, 40 weight parts, 20 weight parts, 8 weight parts, the E1 of 8 weight parts and 25 weight parts is mixed, through double-screw extruding pelletizing;
By the product of above-mentioned gained, in 190 DEG C of vacuum injections in mould, keep this temperature after 5 hours, then cooling curing obtain.
Embodiment 8
After the F1 of the D4 of the C4 of the B1 of the A2 of 100 weight parts, 35 weight parts, 20 weight parts, 8 weight parts, the E1 of 8 weight parts and 25 weight parts is mixed, through double-screw extruding pelletizing;
By the product of above-mentioned gained, in 190 DEG C of vacuum injections in mould, keep this temperature after 5 hours, then cooling curing obtain.
Embodiment 9
After the F1 of the D4 of the C4 of the B1 of the A2 of 100 weight parts, 35 weight parts, 25 weight parts, 9 weight parts, the E1 of 9 weight parts and 25 weight parts is mixed, through double-screw extruding pelletizing;
By the product of above-mentioned gained, in 190 DEG C of vacuum injections in mould, keep this temperature after 5 hours, then cooling curing obtain.
Embodiment 10
After the F1 of the D4 of the C4 of the B1 of the A2 of 100 weight parts, 35 weight parts, 28 weight parts, 9 weight parts, the E1 of 9 weight parts and 28 weight parts is mixed, through double-screw extruding pelletizing;
By the product of above-mentioned gained, in 190 DEG C of vacuum injections in mould, keep this temperature after 5 hours, then cooling curing obtain.
Embodiment 11
After the F1 of the D4 of the C4 of the B1 of the A2 of 100 weight parts, 35 weight parts, 28 weight parts, 9 weight parts, the E1 of 9 weight parts and 30 weight parts is mixed, through double-screw extruding pelletizing;
By the product of above-mentioned gained, in 190 DEG C of vacuum injections in mould, keep this temperature after 5 hours, then cooling curing obtain.
Comparative example 1
After the F1 of the B1 of the A2 of 100 weight parts, 40 weight parts, the E1 of 8 weight parts and 25 weight parts is mixed, through double-screw extruding pelletizing;
By the product of above-mentioned gained, in 190 DEG C of vacuum injections in mould, keep this temperature after 5 hours, then cooling curing obtain.
Comparative example 2
After the F1 of the C4 of the B1 of the A2 of 100 weight parts, 40 weight parts, 20 weight parts, the E1 of 8 weight parts and 25 weight parts is mixed, through double-screw extruding pelletizing;
By the product of above-mentioned gained, in 190 DEG C of vacuum injections in mould, keep this temperature after 5 hours, then cooling curing obtain.
Comparative example 3
After the F1 of the D4 of the B1 of the A2 of 100 weight parts, 40 weight parts, 8 weight parts, the E1 of 8 weight parts and 25 weight parts is mixed, through double-screw extruding pelletizing;
By the product of above-mentioned gained, in 190 DEG C of vacuum injections in mould, keep this temperature after 5 hours, then cooling curing obtain.
Comparative example 4
Similar to embodiment 11, difference is only not adopt vacuum injection.
testing method
Tensile property: tensile strength and elongation at break measure according to JISK6251.
Weather resistance: according to the program of the SA method of JISK6266, carries out degeneration experiment to track traffic pad.Make the side structure-oriented carbon lamp light source of TPE composition, experimental temperature 63 DEG C, this light of continuous irradiation, and water is sprayed on the surface, circulation in every 102 minutes 18 minutes.Annealing time is 48 hours, 96
Hour and 168 hours.Constant strain fatigue experiment is carried out to each sample after experiment of degenerating, at 20 DEG C, with the circulation of 6.7Hz, 40% is applied to sample repeat elongation strain and evaluate its endurance quality.The terminal evaluated is considered to when splitting in surface.Repeat fatigue and cyclic with 1,000 ten thousand times to stop evaluating.
Test result is in table 1.
Table 1
Above data can be found out, compared with not using the product of sulfonated polyimide-silicone copolymers and amino-terminated polybenzimidazole prepolymer, track traffic pad of the present invention has higher intensity and better weather resistance, because herein is provided Advantageous Effects of the present invention.
Aforesaid example is only illustrative, for explaining some features of feature of the present disclosure.Appended claim is intended to the scope wide as far as possible that requirement it is contemplated that, and the embodiment presented herein is only the explanation of the embodiment of the selection of combination according to all possible embodiment.Therefore, the purpose of applicant is the selectional restriction that appended claim is not illustrated the example of feature of the present invention.And progress in science and technology is not replaced to be formed due to the inaccurate reason of language performance by the possible equivalent considered at present or son, and these changes also should be interpreted as being covered by appended claim in the conceived case.
Claims (10)
1. high-performance TPE track traffic pad, is prepared from by the raw material comprising following weight part:
Maleic anhydride modified SEBS100
PP20～50
Sulfonated polyimide-silicone copolymers 10 ~ 30
Amino-terminated polybenzimidazole prepolymer 5 ~ 10
Titanium dioxide 0.1 ~ 10
Viscosity modifier 1 ~ 40.
2. high-performance TPE track traffic pad as claimed in claim 1, wherein, in described maleic anhydride modified SEBS, the percentage of grafting of maleic anhydride is 1 ~ 3%.
3. high-performance TPE track traffic pad as claimed in claim 1, wherein, described sulfonated polyimide-silicone copolymers is by amino-terminated sulfonated polyimide prepolymer and silicone-containing dianhydride 1:(0.8 ~ 1.2 in molar ratio) prepare.
4. high-performance TPE track traffic pad as claimed in claim 3, wherein, described amino-terminated sulfonated polyimide prepolymer is 1:(0.8 ~ 0.98 by sulfonated diamine and dianhydride in molar ratio) prepare.
5. high-performance TPE track traffic pad as claimed in claim 4, wherein, described sulfonated diamine is selected from 4,4'-diamino-diphenyl-2,2'-disulfonic acid, 4,4'-diamino-3,3'-dimethyl diphenyl methane-2,2'-disulfonic acid, 4,4'-diamino-2,2', 3,3'-dimethyl diphenyl methane-2,2'-disulfonic acid, 4,4'-diamino-2,2'-dimethyl diphenyl-2,2'-disulfonic acid, 4,4'-diamino-3,3'-dimethyl diphenyl-2,2'-disulfonic acid, 4,4'-benzidine-3,3'-disulfonic acid, 2,6'-diaminostilbene, 3,5-tri-methyl p-toluenesulfonate, 3,5-diamino benzene sulfonic acid, 4,4'-diaminodiphenyl oxide-2,2'-disulfonic acid, 3,4'-diaminodiphenyl oxide-2,3'-disulfonic acid, 4,4'-diaminostilbene ' ', 3'' bis-phenoxy group benzene-5''-sulfonic acid, 3,3'-diaminostilbene ' ', 3''-bis-phenoxy group benzene-5''-sulfonic acid, two (4-aminophenyl) fluorenes-2, the 7'-disulfonic acid of 9,9'-, 4,4'-diamino-4'', 4'''-bis-aminophenoxy biphenyl-3'', 3'''-disulfonic acid, 4,4'-diamino-4'', 4'''-bis-phenoxy groups-phenylbenzene isopropyl alkane-5'', 5'''-disulfonic acid or 4,4'-diaminostilbene ' ', 4''-bis-phenoxy groups-benzene-2''-sulfonic acid, 2,2 '-bis-(4-sulfonic group phenoxy group) biphenyl sulfonated diamine, in 3,3 '-bis-(4-sulfonic group phenoxy group) biphenyl sulfonated diamine any one or multiple.
6. high-performance TPE track traffic pad as claimed in claim 4, wherein, described dianhydride is selected from pyromellitic dianhydride, 3,4,9,10-perylene tetracarboxylic acid acid anhydride, 4,4'-(hexafluoro isopropyl alkene) two anhydride phthalic acids, the pungent-7-alkene-2,3,5 of dicyclo [2.2.2], 6-tetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 1, in 4,5,8-naphthalenetetracarbacidic acidic dianhydride any one or multiple.
7. high-performance TPE track traffic pad as claimed in claim 1, wherein, described amino-terminated polybenzimidazole prepolymer is 1:(0.8 ~ 0.98 by tetramine and diacid in molar ratio) prepare.
8. high-performance TPE track traffic pad as claimed in claim 7, wherein, described tetramine is selected from 3,3'-diaminobenzidine, 3,3', 4,4'-tetramino phenyl ether, 3,3', 4,4'-tetramino sulfobenzide, 3,3', 4,4'-tetramino benzophenone, 1,2,4,5-tetramino benzene, 1, in 2,5,6-tetramino naphthalene any one or multiple.
9. high-performance TPE track traffic pad as claimed in claim 7, wherein, described diacid is selected oneself diacid, pentanedioic acid, pimelic acid, sebacic acid, dodecanedioic acid, terephthalic acid, m-phthalic acid, 2, in 2'-biphenyl dicarboxylic acid and 4,4'-biphenyl dicarboxylic acid any one or multiple.
10. a preparation method for high-performance TPE track traffic pad, comprises the following steps:
(1) by after the feed composition mixing described in any one of claim 1 ~ 9, through double-screw extruding pelletizing;
(2) by the product of step (1) gained, in 170 DEG C ~ 200 DEG C vacuum injections in mould, then cooling curing obtains.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105647446A (en) * | 2016-01-20 | 2016-06-08 | 上海嘉好胶粘制品有限公司 | Label glue for express waybill and preparation method thereof |
| CN106189820A (en) * | 2016-08-11 | 2016-12-07 | 北京佑琳生科技有限公司 | A kind of radioprotective water-water multi-color |
| CN106366905A (en) * | 2016-08-22 | 2017-02-01 | 北京佑琳生科技有限公司 | Cable fireproofing coating |
| WO2020022356A1 (en) * | 2018-07-27 | 2020-01-30 | 大阪ガスケミカル株式会社 | Thermoplastic composition and molded article thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008052568A1 (en) * | 2006-11-03 | 2008-05-08 | Nanon A/S | A method of producing an article comprising an interpenetrating polymer network (ipn) and an article comprising an ipn |
| CN101879331A (en) * | 2010-06-26 | 2010-11-10 | 上海交通大学 | Preparation method of amino-terminated hyperbranched polybenzimidazole composite film |
| CN102842726A (en) * | 2011-06-21 | 2012-12-26 | 东丽纤维研究所（中国）有限公司 | Silsesquioxane hybridized sulfonated polyimide proton exchange membrane and its preparation method |
| CN104817803A (en) * | 2015-04-16 | 2015-08-05 | 安徽雄亚塑胶科技有限公司 | High-weather-resistance, high-strength and high-wear-resistance high-speed rail shim and preparation method thereof |
-
2015
- 2015-09-29 CN CN201510632975.0A patent/CN105199292A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008052568A1 (en) * | 2006-11-03 | 2008-05-08 | Nanon A/S | A method of producing an article comprising an interpenetrating polymer network (ipn) and an article comprising an ipn |
| CN101879331A (en) * | 2010-06-26 | 2010-11-10 | 上海交通大学 | Preparation method of amino-terminated hyperbranched polybenzimidazole composite film |
| CN102842726A (en) * | 2011-06-21 | 2012-12-26 | 东丽纤维研究所（中国）有限公司 | Silsesquioxane hybridized sulfonated polyimide proton exchange membrane and its preparation method |
| CN104817803A (en) * | 2015-04-16 | 2015-08-05 | 安徽雄亚塑胶科技有限公司 | High-weather-resistance, high-strength and high-wear-resistance high-speed rail shim and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 李恒德: "《现代材料科学与工程辞典》", 31 August 2001, 山东科学技术出版社 * |
| 潘祖仁: "《高分子化学 第4版》", 31 July 2007, 化学工业出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105647446A (en) * | 2016-01-20 | 2016-06-08 | 上海嘉好胶粘制品有限公司 | Label glue for express waybill and preparation method thereof |
| CN106189820A (en) * | 2016-08-11 | 2016-12-07 | 北京佑琳生科技有限公司 | A kind of radioprotective water-water multi-color |
| CN106366905A (en) * | 2016-08-22 | 2017-02-01 | 北京佑琳生科技有限公司 | Cable fireproofing coating |
| WO2020022356A1 (en) * | 2018-07-27 | 2020-01-30 | 大阪ガスケミカル株式会社 | Thermoplastic composition and molded article thereof |
| JPWO2020022356A1 (en) * | 2018-07-27 | 2021-08-02 | 大阪ガスケミカル株式会社 | Thermoplastic composition and its molded article |
| JP7281466B2 (en) | 2018-07-27 | 2023-05-25 | 大阪ガスケミカル株式会社 | Thermoplastic composition and molded article thereof |
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