CN107488334B - A kind of compound thermoplastic elastomer and preparation method thereof - Google Patents

A kind of compound thermoplastic elastomer and preparation method thereof Download PDF

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CN107488334B
CN107488334B CN201710134974.2A CN201710134974A CN107488334B CN 107488334 B CN107488334 B CN 107488334B CN 201710134974 A CN201710134974 A CN 201710134974A CN 107488334 B CN107488334 B CN 107488334B
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glycol
thermoplastic elastomer
polyurethane
segment
polyadipate
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CN107488334A (en
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程睿
管祎嗣
何三雄
南建举
刘森林
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Zhejiang Yi Xin New Mstar Technology Ltd
Shanghai Yitan New Material Co Ltd
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Zhejiang Yi Xin New Mstar Technology Ltd
Shanghai Yitan New Material Co Ltd
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Abstract

The present invention relates to a kind of compound thermoplastic elastomer and preparation method thereof, component and content are as follows: 5~20 parts by weight of styrenic thermoplastic elastomer；10~30 parts by weight of mineral oil；30~50 parts by weight of conjugated polyester resin；1~10 parts by weight of compatilizer；15~35 parts by weight of mineral filler；0~2 parts by weight of stabilizer；0~2 parts by weight of lubricant；10~20 parts by weight of polyurethane.Compound thermoplastic elastomer of the invention passes through the compound acquisition permanent anti-static ability of conjugated polyester resin and styrene analog thermoplastic elastomer, it avoids by the precipitation of addition antistatic agent and with the defect that time antistatic property gradually fails, while there is faster shaping speed and splendid appearance.In addition benzimidazole structure is introduced in polyurethane of the invention, polyurethane is compound with styrenic thermoplastic elastomer, realize that the resistance to permanent compression set performance of styrenic thermoplastic elastomer gets a promotion.

Description

A kind of compound thermoplastic elastomer and preparation method thereof
Technical field
The invention belongs to thermoplastic elastomer (TPE) fields, and in particular to a kind of compound thermoplastic elastomer and preparation method thereof, It is more particularly to a kind of styrenic thermoplastic elastomer and preparation method thereof.
Background technique
Thermoplastic elastomer (TPE) is a kind of high molecular material, it has the high resiliency of rubber at normal temperature, while at high temperature Machinability with plastics.With the development of technology, thermoplastic elastomer (TPE) automobile, building, sports goods, medical apparatus, Applying for the fields such as electronic apparatus, articles for daily use is constantly expanding.But thermoplastic elastomer (TPE) is quiet in the presence of resisting in use The problem of electricity, permanent compression set difference, leads to the disadvantage that thermoplastic elastomer (TPE) surface is easily covered with dust, resilience is poor, limits Its use extensively sent out.
Antistatic macromolecule material can prevent charge, and the upper effect accumulated is known as antistatic property on the surface of the material, has The high molecular material of certain electric conductivity all has anti-charge accumulated effect, and mechanism is to utilize its conductive capability by stored charge It discharges rapidly.It is generally believed that the surface resistivity of material is 106~108There is antistatic effect when Ω.
In practical application, antistatic macromolecule material is mostly that surface recombination conductive layer or filling conductive filler agent are answered Condensation material, conductive filler agent include anionic, cationic organic salt, non-ionic polyol and metal and carbon black filled Agent.Antistatic thermoplastic elastomer is one of antistatic macromolecule material.Chinese patent CN102372894A passes through addition Antistatic agent glycerol single-stearic acyl ester or ethoxylated amine and [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythrite come Antistatic effect is obtained, Chinese patent CN102134365A is obtained by the way that addition polyether-based polymers and alkali metal salt are compound Ionomer antistatic agent obtains antistatic effect.
Have the defects that certain however, obtaining elastomer by the method for adding antistatic agent, is exactly antistatic agent in day With the migration of additive during being often used, antistatic effect is gradually decreased or even is disappeared.
In order to improve the mechanical property of thermoplastic elastomer (TPE), polyurethane, polyurethane are added in thermoplastic elastomer (TPE) It (TPU) is that one kind is made of soft segment (soft segment) and rigid chain segment (hard section), soft segment is responsible for providing the low temperature flexibility of material, Hard section forms physics crosslinking points, inhibits strand sliding, provides the mechanical performance of material.TPU has good processing performance, Hardness range is wide, oil resistant, solvent resistant, wear-resisting, is the good selection of various engineering material.But outdoor ultraviolet light drop in the prior art Solution can be further exacerbated by the compression set of TPU, and urethane bond is easy under prolonged ultraviolet light in TPU It is broken, causes TPU molecular chain degradation, will cause mechanical strength decline, since urethane bond is providing molecule interchain The hard section region of active force is most enriched with, therefore will cause the active force decline of molecule interchain again, is further influenced compression and is permanently become Shape.
Currently, the main solution for compression set of the TPU under action of ultraviolet light is cross-linking modified The organic uv absorbers such as benzotriazole, benzophenone or triazines and the organic light stabilizer of hindered amines are added simultaneously And the inorganic light stabilizer such as nano-titanium dioxide, zinc oxide, on the one hand it is cross-linking modified increase it is mutual between TPU strand Active force, another aspect additive reduce ultraviolet light to the degradation of TPU.However, organic uv absorbers and light are stablized Agent is often poor with the compatibility of polyurethane body, and certain time can not only influence product from the inwardly facing surface precipitation of product later Appearance and also the ultraviolet-resistent property of product is weakened significantly.And the inorganic light stabilizer such as nano-titanium dioxide, zinc oxide is poly- It often will appear reunion when adding in urethane elastomer and dispersion be uneven, so that nano effect can not play, uvioresistant ability is big Big decline.In addition, the organic or inorganic anti ultraviolet agent of addition often disperse in polyurethane matrix it is relatively wide, be easiest to it is ultraviolet The different surely orientation in the hard section region of degradation forms effective high concentration, limited to hard section region uvioresistant function and effect.
In conclusion compression set of the TPU under action of ultraviolet light is overcome to generally require multiple technologies means at present Combination, one side preparation process is complicated, on the other hand needs to add multiple functions component, excessive, compatibility that there are additive amounts Difference influences the problems such as TPU self performance, therefore, how to adopt the TPU for being prepared with simple method good mechanical performance as current Urgent problem to be solved.
Therefore, how to prepare the thermoplastic elastomer (TPE) of the excellent combination properties such as the antistatic, good mechanical performance of one kind is mesh The preceding technical issues that need to address.
Summary of the invention
The purpose of the present invention in view of the deficiencies of the prior art, provides a kind of compound thermoplastic elastomer, and of the invention is compound Polyurethane in thermoplastic elastomer (TPE) is the polyurethane that benzimidazole group is had in molecular backbone, by introducing in polyurethane Benzimidazole structure, polyurethane is compound with styrenic thermoplastic elastomer, realize the resistance to permanent pressure of styrenic thermoplastic elastomer Contracting deformation nature and uvioresistant degradation property get a promotion.Styrenic thermoplastic elastomer of the invention goes back and antistatic agent, obtains Permanent anti-static ability, avoid the precipitation by adding antistatic agent and gradually fail with time antistatic property Defect, while there is faster shaping speed and splendid appearance.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of compound thermoplastic elastomer, component and content are as follows:
The general structure of polyurethane is as follows:
Wherein, R1For-CH2CH2CH2CH2CH2CH2-、
R2For
X is integer, and x=1-10, n are integer, n=3-15；
In general structurePart is the soft segment of polyurethane；
The compound thermoplastic elastomer presses GB/T14522.2008 standard, after ultraviolet light UV340 fluorescent tube aging 96 hours The compression set value of product is 35~45%；
The surface resistivity of the compound thermoplastic elastomer is 106Ω~108Ω, the compound thermoplastic elastomer water Surface resistivity after washing 100 times is 106Ω~108Ω illustrates that the antistatic property of the compound thermoplastic elastomer will not be with The time decaying.
The test voltage of surface resistivity is 500V, time 1min in the present invention, according to ASTMD257-2007 standard Measurement.Washing experimental method be experimental material is immersed in the water cleaned with cotton after be dried under reduced pressure (130MPa, 70 DEG C, 2h), then It is measured after experimental material is placed 24 hours in the environment of 23 DEG C of temperature, humidity 50% with sheet resistance tester.
As a preferred technical scheme:
Compound thermoplastic elastomer as described above, the hardness of the compound thermoplastic elastomer are 30A~85A, product Surface effect is excellent, while having excellent antistatic property and compression set performance；The hardness range of the polyurethane For shore 80A- shore 65D；The polyurethane presses GB/T14522.2008 standard, after ultraviolet light UV340 fluorescent tube aging 96 hours The compression set value of product is less than 30%.
Compound thermoplastic elastomer as described above, the styrenic thermoplastic elastomer be styrene block copolymer or Its hydride, specially Styrene-Butadiene-Styrene Block Copolymer (SBS), styrene-isoprene-phenylethene block Copolymer (SIS), hydrogenated styrene-butadiene-styrene block copolymers (SEBS), hydrogenated styrene isoprene-benzene second One or more of alkene block copolymer (SEPS) or styrene ethylene-propylene-styrene block copolymer (SEEPS)；It is described The weight average molecular weight of styrenic thermoplastic elastomer is 80,000~500,000；
The mineral oil be saturated straight chain alkane oil or be saturated naphthenic oil one or more of；The sudden strain of a muscle of the mineral oil Point is higher than 150 DEG C；
The conjugated polyester resin is TPEE, specially with terephthalic acid (TPA) or its carboxylate, Isosorbide-5-Nitrae butanediol and poly- tetrahydro furan Mutter polyalcohol or polypropylene oxide ethoxylated polyhydric alcohol or poly-epsilon-caprolactone polyalcohol is that terephthalate ternary made from monomer is total Polymers；The number-average molecular weight of the conjugated polyester resin is 20000-30000；
The compatilizer is maleic anhydride-g-SBS；
The mineral filler is calcium carbonate, talcum powder, land plaster, flake asbestos, clay, barium sulfate, mica powder or kaolinite One or more of soil, the average particle size of the mineral filler particle are 0.5~50nm；
The stabilizer be the stabilizer of the functional group containing benzophenone, hindered phenol stabilizer, phosphite ester stabilizer or by Hinder one or more of amine stabiliser；
The lubricant is one or more of fatty acid, fatty acid amide or silicone.
Compound thermoplastic elastomer as described above, the soft segment be polyester diol segment, polyether Glycols segment or The mixing segment of polyester diol and polyether Glycols, the polyester diol segment are polyethylene glycol adipate segment, gather Adipic acid -1,4- butanediol ester segment, polyadipate -1,6-HD ester segment, polyadipate ethylene glycol -1,4- butanediol ester Segment, polyadipate ethylene glycol -1,6-HD ester segment, gather polyadipate -1,4- butanediol -1,6-HD ester segment Adipate glycol-propylene glycol ester segment, polyadipate diglycol ester segment, polycaprolactone segment, poly- carbonic acid 1,6- Hexylene glycol ester segment, the polyether Glycols segment are polytetrahydrofuran segment or polypropylene glycol segment.
As above the preparation method of any compound thermoplastic elastomer, comprising the following steps: by styrenic thermoplastic After elastomer and mineral oil mixed on low speed, conjugated polyester resin, compatilizer, mineral filler, stabilizer, lubricant and poly- ammonia is added Ester mixed at high speed is then added to double screw extruder, squeezes out, and is granulated and obtains thermoplastic elastomer (TPE)；
Polyurethane the preparation method comprises the following steps:
(1) prepolymerization reaction；
In organic solvent by the polyester diol being dehydrated and/or polyether Glycols dissolution, it is different that organic two are then added Cyanate and catalyst carry out prepolymerization reaction under inert gas protection after mixing；
(2) chain extending reaction；
It is added into prepolymerization reaction system in molecular structure and has the glycol chain extender of benzimidazole group, in indifferent gas Body protection is lower to carry out chain extending reaction, and then drying removal organic solvent obtains in a kind of molecular backbone with benzimidazole group Polyurethane.
The preparation method of compound thermoplastic elastomer as described above, the processing temperature of the double screw extruder are 190 DEG C~250 DEG C, revolving speed 200rpm~300rpm；The speed of the mixed on low speed is 100rpm~450rpm, and the time is 3~5 points Clock；The speed of the mixed at high speed is 900rpm~1500rpm, and the time is 1~3 minute.
The preparation method of compound thermoplastic elastomer as described above, in step (1), the polyester diol is to gather oneself two Sour glycol ester glycol, polyadipate -1,4- butyl glycol ester diol, polyadipate -1,6-HD esterdiol, polyadipate second Glycol -1,4- butyl glycol ester diol, polyadipate ethylene glycol -1,6-HD esterdiol, butanediol -1 polyadipate -1,4-, 6- hexylene glycol esterdiol, polyadipate diglycol esterdiol, gathers in oneself polyadipate ethylene glycol and 1,2-propylene glycol esterdiol Esterdiol or poly- carbonic acid 1,6-HD esterdiol；
The polyether Glycols are polytetrahydrofuran diol or polypropylene glycol；
The organic diisocyanate is 2,6- toluene di-isocyanate(TDI), 2,4 toluene diisocyanate, to two isocyanide of benzene It is acid esters, hexamethylene diisocyanate, diphenyl methane -4,4 '-diisocyanate, cyclohexanedimethyleterephthalate diisocyanate, different Isophorone diisocyanate, benzene dimethylene diisocyanate, 3,3 '-dimethyl -4,4 '-biphenyl diisocyanate, hexamethylene Dimethylene diisocyanate, 4,4 '-dicyclohexyl methyl hydride diisocyanates, naphthalene -1,5- diisocyanate or 3,3 '-diformazans Base -4,4 '-methyl diphenylene diisocyanate；
The temperature of the prepolymerization reaction is 50-120 DEG C, and the reaction time is 2-5 hours；The organic solvent is N, N- bis- Methylformamide, DMAC N,N' dimethyl acetamide or dimethyl sulfoxide；
The catalyst is one of trimethylamine or metal organic acid salt or a variety of, and wherein metal organic acid salt is Bismuth, tin, titanium, lead, zinc, potassium, antimony, cobalt, iron, nickel, molybdenum, vanadium, manganese or zirconium acylate；The inert gas be nitrogen, helium, Neon, argon gas, Krypton or xenon；
The trimethylamine is triethylamine, triethylenediamine, N-ethylmorpholine or N, N- dimethylethanolamine；The gold Category acylate is bismuth neodecanoate, bismuth naphthenate, isooctyl acid bismuth, stannous octoate, dibutyl tin dilaurate, four isopropyl of metatitanic acid Ester, tetrabutyl titanate, isooctyl acid lead, zinc Isoocatanoate, zinc naphthenate, isooctyl acid potassium, potassium acetate, potassium oleate, antimony acetate, cycloalkanes Sour cobalt, ferric acetyl acetonade, nickel acetate, molybdenum naphthenate, vanadium iso-octoate, manganese acetate or acetylacetone,2,4-pentanedione zirconium.
The preparation method of compound thermoplastic elastomer as described above, when with prepolymerization reaction polyester binary used it is pure and mild/ Or on the basis of the gross mass of polyether Glycols, the additive amount of the catalyst is 15-500ppm；Gather in the prepolymerization reaction system The concentration of ester dihydric alcohol and/or polyether Glycols is 50-67wt%.
The preparation method of compound thermoplastic elastomer as described above, in step (2), the temperature of the chain extending reaction is 80-120 DEG C, the reaction time is 3-7 hours；Glycol chain extender in the molecular structure with benzimidazole group is 1H- Benzimidazole -4,6- glycol, 1H- benzimidazole -5,6- glycol, 1H- benzimidazole -4,7- glycol or bis- (the 1H- benzos of 1,2- Imidazoles -2- base) ethane -1,2- glycol；The inert gas is nitrogen, helium, neon, argon gas, Krypton or xenon；The drying The temperature for removing organic solvent is 100-120 DEG C, and the time is 10-12 hours.
The preparation method of compound thermoplastic elastomer as described above, the polyester binary being added when being reacted is pure and mild/ Or the gross mass of the glycol chain extender in polyether Glycols, organic diisocyanate and molecular structure with benzimidazole group On the basis of, polyester diol and/or polyether Glycols account for the percentage of gross mass as 40-60%, and organic diisocyanate Zhan is total The percentage of quality is 30-40%, and the glycol chain extender with benzimidazole group accounts for the percentage of gross mass in molecular structure Than being the combination of arbitrary proportion when the pure and mild polyether Glycols of polyester binary are combination for 10-20%.
Invention mechanism:
Polyurethane compression set under action of ultraviolet light is serious, because acting between non-modified TPU strand Power is weaker, and strand can generate many irreversible slidings in compression process and make to produce irreversible compressive deformation It is bigger than normal at compression set value, and urethane bond is easy to be broken under prolonged ultraviolet light in TPU, Cause TPU molecular chain degradation, will cause mechanical strength decline, since urethane bond is providing the hard of molecule interchain active force Section region is most enriched with, therefore will cause the active force decline of molecule interchain again, further influences compression set.The present invention is logical Cross the compression set that benzimidazole group reduction polyurethane is introduced in polyurethane molecular main chain under action of ultraviolet light.By In benzimidazole be it is a kind of containing there are two the benzo-heterocycle compound of nitrogen-atoms, molecular structure is symmetrical, and steric hindrance is big, have Good thermal stability.Being introduced into benzimidazole unit in segmented polyurethane region can use lone pair electrons in its molecule on nitrogen More stable hydrogen bond is formed with the hydrogen atom in hard section strand, increases hydrogen bond density in hard section region, is further increased point Active force between son reduces the sliding of TPU strand, reduces Compression Set.Meanwhile the raising of hydrogen bond density can make firmly Hydrogen atom in section is relatively more stable, and the available inhibition of hydrogen abstraction reaction during photooxidation resistance improves hard section region Ultraviolet light stability avoids the serious degradation in hard section region, compresses forever so as to be effectively improved ultraviolet light and aging process to TPU The influence deformed long.
Styrenic elastomer (SEBS) is that the three block that styrene segment, butadiene segment, styrene segment are formed is total Polymers.Wherein styrene segment belongs to hard section, and cohesive energy is larger, is mutually associated formation by noncovalent interactions such as Van der Waals forces Manage crosslinking points；Soft segment is butadiene segment, then is the biggish high resiliency segment of the ability that rotates freely.Hard section aggregation is mutually dispersed in soft Between the continuous phase matrix that section (rubber segments) is formed, morphologically belong to microcosmic heterogeneous structure.At normal temperature, hard section not only acts as solid Determine the physical crosslinking effect of soft segment (elastomeric segments), while also generating reinforcing effect, moreover, this " physics " crosslinking is with reversible Property, i.e., restraining force is lost at high temperature, is in plasticity；When temperature is down to room temperature, crosslinking restores again, plays similar vulcanized rubber crosslinking points Effect.The present invention introduces polyurethane on the basis of styrenic elastomer, the object formed by styrenic elastomer It is interlaced to manage the physical cross-linked network that cross-linked network and polyurethane are formed, forms more three-dimensional tridimensional network to obtain The more preferably performance of compression set.
Compound thermoplastic elastomer of the invention is on the one hand due to the addition of copolyesters, and wherein ehter bond is there are lone pair electrons, Receive proton ability with certain, to realize antistatic effect by the proton transfer of therein；On the other hand exist The molecule segment that alcohols is introduced in copolyesters, the molecule segment containing alcohols have stronger hydrophilic ability to be conducive to improve heat The antistatic property of Plastic resilient composition.
The utility model has the advantages that
Compound thermoplastic elastomer of the invention is obtained by conjugated polyester resin and the compound of styrene analog thermoplastic elastomer Permanent anti-static ability, avoid the precipitation by adding antistatic agent and gradually fail with time antistatic property Defect, while there is faster shaping speed and splendid appearance.
In addition benzimidazole structure is introduced in polyurethane of the invention, polyurethane and styrenic thermoplastic elastomer is answered It closes, realizes that the resistance to permanent compression set performance of styrenic thermoplastic elastomer gets a promotion.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Fixed range.
Embodiment 1
A kind of preparation method of polyurethane, comprising the following steps:
(1) prepolymerization reaction；
The polyethylene glycol adipate glycol being dehydrated is dissolved in n,N-Dimethylformamide, is then added 2,6- Toluene di-isocyanate(TDI) and triethylamine carry out prepolymerization reaction under nitrogen protection after mixing, and the temperature of prepolymerization reaction is 50 DEG C, the reaction time is 2 hours, on the basis of the gross mass of polyethylene glycol adipate glycol used when prepolymerization reaction, three second The additive amount of amine is 15ppm, and the concentration of polyethylene glycol adipate glycol is 50wt% in prepolymerization reaction system；
(2) chain extending reaction；
1H- benzimidazole -4,6- glycol is added into prepolymerization reaction system, carries out chain extending reaction under nitrogen protection, expands The temperature of chain reaction is 80 DEG C, and the reaction time is 3 hours, the polyethylene glycol adipate glycol being added when being reacted, 2, On the basis of the gross mass of 6- toluene di-isocyanate(TDI) and 1H- benzimidazole -4,6- glycol, polyethylene glycol adipate glycol Zhan is total The percentage of quality is 40%, and the percentage that 2,6- toluene di-isocyanate(TDI)s account for gross mass is 40%, 1H- benzimidazole -4,6- The percentage that glycol accounts for gross mass is 20%, finally removes organic solvent 10 hours in 100 DEG C of drying and obtains a kind of molecular backbone In have benzimidazole group polyurethane.
The general structure of final polyurethane obtained is as follows:
Wherein, R1ForR2ForIn general structurePart is polyurethane Soft segment, soft segment is polyethylene glycol adipate segment, and x=1, n=3 in general structure crush polyurethane obtained above It is granulated and is molded into the standard testing batten with a thickness of 2mm through injection molding machine by ASTM D412 standard, then press GB/ T14522.2008 standard appendix C table C.1 exposure cycles Class1, is pressed using taking out after ultraviolet light UV340 fluorescent tube aging 96 hours Testing its compression set value (100 DEG C/for 24 hours) according to ASTM D395 is 29.8%, and the hardness of polyurethane is shore 65D.
Embodiment 2
A kind of preparation method of polyurethane, comprising the following steps:
(1) prepolymerization reaction；
The polyadipate being dehydrated -1,4-butanediol esterdiol is dissolved in n,N-Dimethylformamide, is then added 2,4- toluene di-isocyanate(TDI)s and triethylenediamine carry out prepolymerization reaction under nitrogen protection after mixing, prepolymerization reaction Temperature is 55 DEG C, and the reaction time is 2.2 hours, and polyadipate used -1,4-butanediol esterdiol is total when with prepolymerization reaction On the basis of quality, the additive amount of triethylenediamine is 36ppm, polyadipate -1,4-butanediol ester two in prepolymerization reaction system The concentration of alcohol is 51wt%；
(2) chain extending reaction；
1H- benzimidazole -4,6- glycol is added into prepolymerization reaction system, carries out chain extending reaction under nitrogen protection, expands The temperature of chain reaction is 83 DEG C, and the reaction time is 3.3 hours, the polyadipate-Isosorbide-5-Nitrae-butanediol ester being added when being reacted On the basis of the gross mass of glycol, 2,4- toluene di-isocyanate(TDI) and 1H- benzimidazole -4,6- glycol, polyadipate-Isosorbide-5-Nitrae-fourth two The percentage that alcohol esterdiol accounts for gross mass is 42%, and the percentage that 2,4- toluene di-isocyanate(TDI)s account for gross mass is 40%, 1H- benzene And it is 18% that imidazoles -4,6- glycol, which accounts for the percentage of gross mass, finally removes organic solvent 10 hours in 102 DEG C of drying and obtains one The polyurethane of benzimidazole group is had in kind molecular backbone.
The general structure of final polyurethane obtained is as follows:
Wherein, R1ForR2ForIn general structurePart is the soft of polyurethane Section, soft segment are polyadipate -1,4-butanediol ester segment, and x=2 in general structure, n=4, polyurethane uses and 1 phase of embodiment The compression set value that same test method measures is 29.2%, and the hardness of polyurethane is shore 55D.
Embodiment 3
A kind of preparation method of polyurethane, comprising the following steps:
(1) prepolymerization reaction；
Polyadipate -1, the 6- hexylene glycol esterdiol being dehydrated is dissolved in n,N-Dimethylformamide, is then added Paraphenylene diisocyanate and N-ethylmorpholine carry out prepolymerization reaction under helium protection after mixing, and the temperature of prepolymerization reaction is 60 DEG C, the reaction time is 2.5 hours, and the gross mass of polyadipate -1,6- hexylene glycol esterdiol used is when with prepolymerization reaction Benchmark, the additive amount of N-ethylmorpholine are 70ppm, the concentration of polyadipate -1,6- hexylene glycol esterdiol in prepolymerization reaction system For 52wt%；
(2) chain extending reaction；
1H- benzimidazole -4,6- glycol is added into prepolymerization reaction system, carries out chain extending reaction under helium protection, expands The temperature of chain reaction is 86 DEG C, and the reaction time is 3.6 hours, polyadipate -1, the 6- hexylene glycol ester being added when being reacted On the basis of the gross mass of glycol, paraphenylene diisocyanate and 1H- benzimidazole -4,6- glycol, polyadipate -1,6- hexylene glycol ester The percentage that glycol accounts for gross mass is 44%, and the percentage that paraphenylene diisocyanate accounts for gross mass is 39%, 1H- benzimidazole- The percentage that 4,6- glycol account for gross mass is 17%, finally removes organic solvent 10 hours in 103 DEG C of drying and obtains a kind of molecule The polyurethane of benzimidazole group is had in main chain.
The general structure of final polyurethane obtained is as follows:
Wherein, R1ForR2ForIn general structurePart is polyurethane Soft segment, soft segment is polyadipate -1,6- hexylene glycol ester segment, and x=2 in general structure, n=5, polyurethane uses and embodiment The compression set value that 1 identical test method measures is 29%, and the hardness of polyurethane is shore 98A.
Embodiment 4
A kind of preparation method of polyurethane, comprising the following steps:
(1) prepolymerization reaction；
The polyadipate being dehydrated ethylene glycol -1,4-butanediol esterdiol is dissolved in n,N-Dimethylformamide, so After be added 1, hexamethylene-diisocyanate and N, N- dimethylethanolamine carry out prepolymerization reaction under helium protection after mixing, in advance The temperature of poly- reaction is 65 DEG C, and the reaction time is 2.7 hours, polyadipate used ethylene glycol-Isosorbide-5-Nitrae-fourth when with prepolymerization reaction On the basis of the gross mass of glycol esterdiol, N, the additive amount of N- dimethylethanolamine is 105ppm, gathers oneself in prepolymerization reaction system The concentration of diacid ethylene glycol -1,4- butyl glycol ester diol is 54wt%；
(2) chain extending reaction；
1H- benzimidazole -5,6- glycol is added into prepolymerization reaction system, carries out chain extending reaction under helium protection, expands The temperature of chain reaction is 89 DEG C, and the reaction time is 3.8 hours, the polyadipate ethylene glycol-Isosorbide-5-Nitrae-fourth being added when being reacted On the basis of the gross mass of glycol esterdiol, 1, hexamethylene-diisocyanate and 1H- benzimidazole -5,6- glycol, polyadipate second two The percentage that alcohol -1,4-butanediol esterdiol accounts for gross mass is 45%, 1, and the percentage that hexamethylene-diisocyanate accounts for gross mass is The percentage that 38%, 1H- benzimidazole -5,6- glycol account for gross mass is 17%, finally removes organic solvent in 105 DEG C of drying Obtain within 10 hours the polyurethane that benzimidazole group is had in a kind of molecular backbone.
The general structure of final polyurethane obtained is as follows:
Wherein, R1For-CH2CH2CH2CH2CH2CH2, R2ForIn general structurePart For the soft segment of polyurethane, soft segment is polyadipate ethylene glycol -1,4-butanediol ester segment, x=3, n=6 in general structure, poly- ammonia For the compression set value that ester uses test method same as Example 1 to measure for 28.8%, the hardness of polyurethane is shore 95A。
Embodiment 5
A kind of preparation method of polyurethane, comprising the following steps:
(1) prepolymerization reaction；
Polyadipate ethylene glycol -1, the 6- hexylene glycol esterdiol being dehydrated is dissolved in n,N-Dimethylformamide, so 4,4 '-diisocyanate of diphenyl methane-and bismuth neodecanoate are added afterwards and carries out prepolymerization reaction under neon protection after mixing, The temperature of prepolymerization reaction is 70 DEG C, and the reaction time is 3.0 hours, polyadipate ethylene glycol -1,6- used when with prepolymerization reaction On the basis of the gross mass of hexylene glycol esterdiol, the additive amount of bismuth neodecanoate is 130ppm, polyadipate second in prepolymerization reaction system Glycol -1,6-HD esterdiol concentration is 55wt%；
(2) chain extending reaction；
1H- benzimidazole -5,6- glycol is added into prepolymerization reaction system, carries out chain extending reaction under neon protection, expands The temperature of chain reaction be 92 DEG C, the reaction time be 4.0 hours, the polyadipate ethylene glycol -1,6- being added when being reacted oneself On the basis of the gross mass of glycol esterdiol, 4,4 '-diisocyanate of diphenyl methane-and 1H- benzimidazole -5,6- glycol, gather The percentage that adipate glycol -1,6- hexylene glycol esterdiol accounts for gross mass is 46%, 4,4 '-diisocyanate of diphenyl methane - It is the percentage that 37%, 1H- benzimidazole -5,6- glycol accounts for gross mass is 17% that ester, which accounts for the percentage of gross mass, finally 107 DEG C drying removal obtains the polyurethane that benzimidazole group is had in a kind of molecular backbone for organic solvent 11 hours.
The general structure of final polyurethane obtained is as follows:
Wherein, R1ForR2ForIn general structure Part is the soft segment of polyurethane, and soft segment is polyadipate ethylene glycol -1,6- hexylene glycol ester segment, x=3, n=6 in general structure, For 28.6%, the hardness of polyurethane is the compression set value that polyurethane uses test method same as Example 1 to measure Shore 95A.
Embodiment 6
A kind of preparation method of polyurethane, comprising the following steps:
(1) prepolymerization reaction；
Polyadipate -1,4- butanediol -1,6-HD the esterdiol being dehydrated is dissolved in DMAC N,N' dimethyl acetamide In, cyclohexanedimethyleterephthalate diisocyanate and bismuth naphthenate is then added, and progress pre-polymerization is anti-under neon protection after mixing It answers, the temperature of prepolymerization reaction is 75 DEG C, and the reaction time is 3.2 hours, polyadipate-Isosorbide-5-Nitrae-fourth two used when with prepolymerization reaction On the basis of the gross mass of alcohol -1,6- hexylene glycol esterdiol, the additive amount of bismuth naphthenate is 170ppm, gathers oneself in prepolymerization reaction system Diacid -1,4- butanediol -1,6-HD esterdiol concentration is 56wt%；
(2) chain extending reaction；
1H- benzimidazole -5,6- glycol is added into prepolymerization reaction system, carries out chain extending reaction under neon protection, expands The temperature of chain reaction is 95 DEG C, and the reaction time is 4.3 hours, the polyadipate-Isosorbide-5-Nitrae-butanediol-being added when being reacted The gross mass of 1,6-HD esterdiol, cyclohexanedimethyleterephthalate diisocyanate and 1H- benzimidazole -5,6- glycol is base Standard, the percentage that polyadipate -1,4-butanediol -1,6- hexylene glycol esterdiol accounts for gross mass is 48%, cyclohexanedimethyleterephthalate It is the percentage that 36%, 1H- benzimidazole -5,6- glycol accounts for gross mass is 16% that diisocyanate, which accounts for the percentage of gross mass, Finally the polyurethane that benzimidazole group is had in a kind of molecular backbone is obtained within organic solvent 11 hours in 109 DEG C of drying removals.
The general structure of final polyurethane obtained is as follows:
Wherein, R1ForR2ForIn general structurePart is The soft segment of polyurethane, soft segment are polyadipate -1,4-butanediol -1,6- hexylene glycol ester segment, x=4, n=7 in general structure, For 28.5%, the hardness of polyurethane is the compression set value that polyurethane uses test method same as Example 1 to measure Shore 92A.
Embodiment 7
A kind of preparation method of polyurethane, comprising the following steps:
(1) prepolymerization reaction；
The polyadipate ethylene glycol and 1,2-propylene glycol esterdiol being dehydrated is dissolved in n,N-dimethylacetamide, then plus Enter isophorone diisocyanate and isooctyl acid bismuth carries out prepolymerization reaction, the temperature of prepolymerization reaction under protection of argon gas after mixing Degree is 80 DEG C, and the reaction time is 3.5 hours, and polyadipate ethylene glycol and 1,2-propylene glycol esterdiol used is total when with prepolymerization reaction On the basis of quality, the additive amount of isooctyl acid bismuth is 200ppm, polyadipate ethylene glycol and 1,2-propylene glycol esterdiol in prepolymerization reaction system Concentration be 58wt%；
(2) chain extending reaction；
1H- benzimidazole -5,6- glycol is added into prepolymerization reaction system, carries out chain extending reaction under protection of argon gas, expands The temperature of chain reaction is 98 DEG C, and the reaction time is 4.7 hours, the polyadipate ethylene glycol and 1,2-propylene glycol being added when being reacted On the basis of the gross mass of esterdiol, isophorone diisocyanate and 1H- benzimidazole -5,6- glycol, polyadipate ethylene glycol - The percentage that propylene glycol ester glycol accounts for gross mass is 50%, and the percentage that isophorone diisocyanate accounts for gross mass is 36%, The percentage that 1H- benzimidazole -5,6- glycol accounts for gross mass is 14%, is finally removed organic solvent 11 hours in 110 DEG C of drying Obtain the polyurethane that benzimidazole group is had in a kind of molecular backbone.
The general structure of final polyurethane obtained is as follows:
Wherein, R1ForR2ForIn general structurePart is poly- ammonia The soft segment of ester, soft segment are polyadipate ethylene glycol and 1,2-propylene glycol ester segment, x=4 in general structure, n=8, polyurethane use with The compression set value that the identical test method of embodiment 1 measures is 28.2%, and the hardness of polyurethane is shore 90A.
Embodiment 8
A kind of preparation method of polyurethane, comprising the following steps:
(1) prepolymerization reaction；
The polyadipate diglycol esterdiol being dehydrated is dissolved in n,N-dimethylacetamide, is then added Benzene dimethylene diisocyanate and stannous octoate carry out prepolymerization reaction, the temperature of prepolymerization reaction under protection of argon gas after mixing Degree is 85 DEG C, and the reaction time is 3.8 hours, total matter of polyadipate diglycol esterdiol used when with prepolymerization reaction On the basis of amount, the additive amount of stannous octoate is 230ppm, polyadipate diglycol esterdiol in prepolymerization reaction system Concentration is 59wt%；
(2) chain extending reaction；
1H- benzimidazole -4,7- glycol is added into prepolymerization reaction system, carries out chain extending reaction under protection of argon gas, expands The temperature of chain reaction is 100 DEG C, and the reaction time is 5.0 hours, the polyadipate diglycol being added when being reacted On the basis of the gross mass of esterdiol, benzene dimethylene diisocyanate and 1H- benzimidazole -4,7- glycol, polyadipate one contracts The percentage that diethylene glycol esterdiol accounts for gross mass is 52%, and the percentage that benzene dimethylene diisocyanate accounts for gross mass is The percentage that 35%, 1H- benzimidazole -4,7- glycol account for gross mass is 13%, finally removes organic solvent in 112 DEG C of drying Obtain within 11 hours the polyurethane that benzimidazole group is had in a kind of molecular backbone.
The general structure of final polyurethane obtained is as follows:
Wherein, R1ForR2ForIn general structurePart is the soft of polyurethane Section, soft segment are polyadipate diglycol ester segment, and x=5 in general structure, n=9, polyurethane uses and 1 phase of embodiment The compression set value that same test method measures is 28%, and the hardness of polyurethane is shore 87A.
Embodiment 9
A kind of preparation method of polyurethane, comprising the following steps:
(1) prepolymerization reaction；
The polycaprolactone glycol being dehydrated is dissolved in n,N-dimethylacetamide, 3,3 '-dimethyl -4 are then added, 4 '-biphenyl diisocyanates and dibutyl tin dilaurate carry out prepolymerization reaction under Krypton protection after mixing, and pre-polymerization is anti- The temperature answered is 90 DEG C, and the reaction time is 4.0 hours, and the gross mass of polycaprolactone glycol used is base when using prepolymerization reaction Standard, the additive amount of dibutyl tin dilaurate are 270ppm, and the concentration of polycaprolactone glycol is 60wt% in prepolymerization reaction system；
(2) chain extending reaction；
1H- benzimidazole -4,7- glycol is added into prepolymerization reaction system, carries out chain extending reaction under Krypton protection, expands The temperature of chain reaction is 104 DEG C, and the reaction time is 5.3 hours, the polycaprolactone glycol being added when being reacted, 3,3 '-two On the basis of 4,4 '-biphenyl diisocyanate of methyl-and the gross mass of 1H- benzimidazole -4,7- glycol, polycaprolactone glycol Zhan is total The percentage of quality is 53%, 3,3 '-dimethyl -4, and the percentage that 4 '-biphenyl diisocyanates account for gross mass is 34%, 1H- The percentage that benzimidazole -4,7- glycol accounts for gross mass is 13%, finally removes organic solvent 12 hours and obtains in 113 DEG C of drying The polyurethane of benzimidazole group is had in a kind of molecular backbone.
The general structure of final polyurethane obtained is as follows:
Wherein, R1ForR2ForIn general structurePart is The soft segment of polyurethane, soft segment are polycaprolactone segment, and x=5 in general structure, n=10, polyurethane is using same as Example 1 The compression set value that measures of test method be 27.8%, the hardness of polyurethane is shore 90A.
Embodiment 10
A kind of preparation method of polyurethane, comprising the following steps:
(1) prepolymerization reaction；
The poly- carbonic acid 1 that will be dehydrated, 6- hexylene glycol esterdiol are dissolved in n,N-dimethylacetamide, and hexamethylene is then added Alkane dimethylene diisocyanate and tetraisopropyl titanate carry out prepolymerization reaction, prepolymerization reaction under Krypton protection after mixing Temperature be 95 DEG C, the reaction time be 4.2 hours, poly- carbonic acid 1 used when with prepolymerization reaction, total matter of 6- hexylene glycol esterdiol On the basis of amount, the additive amount of tetraisopropyl titanate is 300ppm, poly- carbonic acid 1 in prepolymerization reaction system, 6- hexylene glycol esterdiol Concentration is 62wt%；
(2) chain extending reaction；
1H- benzimidazole -4,7- glycol is added into prepolymerization reaction system, carries out chain extending reaction under Krypton protection, expands The temperature of chain reaction is 108 DEG C, and the reaction time is 5.6 hours, the poly- carbonic acid 1 being added when being reacted, 6- hexylene glycol ester two On the basis of the gross mass of alcohol, cyclohexanedimethyleterephthalate diisocyanate and 1H- benzimidazole -4,7- glycol, poly- carbonic acid 1,6- oneself The percentage that glycol esterdiol accounts for gross mass is 55%, and the percentage that cyclohexanedimethyleterephthalate diisocyanate accounts for gross mass is The percentage that 33%, 1H- benzimidazole -4,7- glycol account for gross mass is 12%, finally removes organic solvent in 115 DEG C of drying Obtain within 12 hours the polyurethane that benzimidazole group is had in a kind of molecular backbone.
The general structure of final polyurethane obtained is as follows:
Wherein, R1ForR2ForIn general structurePart is The soft segment of polyurethane, soft segment are poly- carbonic acid 1, and 6- hexylene glycol ester segment, x=6 in general structure, n=11, polyurethane uses and reality Applying the compression set value that the identical test method of example 1 measures is 27.6%, and the hardness of polyurethane is shore 87A.
Embodiment 11
A kind of preparation method of polyurethane, comprising the following steps:
(1) prepolymerization reaction；
The polytetrahydrofuran diol being dehydrated is dissolved in dimethyl sulfoxide, 4,4 '-dicyclohexyl methyl hydrides are then added The mixture (mass ratio 1:1) of diisocyanate and triethylamine and triethylenediamine after mixing Krypton protection under into Row prepolymerization reaction, the temperature of prepolymerization reaction are 100 DEG C, and the reaction time is 4.5 hours, poly- tetrahydro furan used when with prepolymerization reaction On the basis of the gross mass of glycol of muttering, the additive amount of the mixture of triethylamine and triethylenediamine is 330ppm, prepolymerization reaction body The concentration of polytetrahydrofuran diol is 63wt% in system；
(2) chain extending reaction；
1H- benzimidazole -4,7- glycol is added into prepolymerization reaction system, carries out chain extending reaction under Krypton protection, expands The temperature of chain reaction is 112 DEG C, and the reaction time is 5.9 hours, the polytetrahydrofuran diol being added when being reacted, 4,4 '- On the basis of the gross mass of dicyclohexyl methyl hydride diisocyanate and 1H- benzimidazole -4,7- glycol, polytetrahydrofuran diol Zhan is total The percentage of quality is 56%, and the percentage that 4,4'-Dicyclohexylmethane diisocyanate accounts for gross mass is 32%, 1H- benzo The percentage that imidazoles -4,7- glycol accounts for gross mass is 12%, finally removes organic solvent 12 hours in 116 DEG C of drying and obtains one The polyurethane of benzimidazole group is had in kind molecular backbone.
The general structure of final polyurethane obtained is as follows:
Wherein, R1ForR2ForIn general structurePortion It is divided into the soft segment of polyurethane, soft segment is polytetrahydrofuran segment, and x=6 in general structure, n=12, polyurethane uses and implementation The compression set value that the identical test method of example 1 measures is 27.5%, and the hardness of polyurethane is shore 85A.
Embodiment 12
A kind of preparation method of polyurethane, comprising the following steps:
(1) prepolymerization reaction；
The polypropylene glycol being dehydrated is dissolved in dimethyl sulfoxide, naphthalene -1,5- diisocyanate and different pungent is then added The mixture (mass ratio 1:2) of lead plumbate and zinc Isoocatanoate carries out prepolymerization reaction under Krypton protection after mixing, and pre-polymerization is anti- The temperature answered is 105 DEG C, and the reaction time is 4.6 hours, different on the basis of the gross mass of polypropylene glycol used when prepolymerization reaction The additive amount of the mixture of lead octoate and zinc Isoocatanoate is 370ppm, and the concentration of polypropylene glycol is in prepolymerization reaction system 65wt%；
(2) chain extending reaction；
Bis- (1H- benzimidazolyl-2 radicals-yl) ethane -1, the 2- glycol of 1,2- are added into prepolymerization reaction system, are protected in Krypton Lower carry out chain extending reaction, the temperature of chain extending reaction are 115 DEG C, and the reaction time is 6.2 hours, poly- third be added when being reacted Glycol, naphthalene -1,5- diisocyanate and 1, on the basis of the gross mass of bis- (1H- benzimidazolyl-2 radicals-yl) ethane -1, the 2- glycol of 2-, The percentage that polypropylene glycol accounts for gross mass is 58%, and the percentage that naphthalene -1,5- diisocyanate accounts for gross mass is 32%, and 1,2- is bis- The percentage that (1H- benzimidazolyl-2 radicals-yl) ethane -1,2- glycol accounts for gross mass is 10%, finally organic in 118 DEG C of drying removals Obtain within solvent 12 hours the polyurethane that benzimidazole group is had in a kind of molecular backbone.
The general structure of final polyurethane obtained is as follows:
Wherein, R1ForR2ForIn general structurePart is the soft segment of polyurethane, and soft segment is polypropylene glycol segment, x=6, n=13 in general structure, poly- ammonia For the compression set value that ester uses test method same as Example 1 to measure for 27.3%, the hardness of polyurethane is shore 82A。
Embodiment 13
A kind of preparation method of polyurethane, comprising the following steps:
(1) prepolymerization reaction；
By the mixture (mass ratio 1:1) for the pure and mild polytetrahydrofuran diol of polyethylene glycol adipate two being dehydrated It is dissolved in dimethyl sulfoxide, 3,3 '-dimethyl -4,4 '-methyl diphenylene diisocyanates and bismuth naphthenate, ring is then added The mixture (mass ratio 1:1:1) of alkanoic acid cobalt and manganese acetate carries out prepolymerization reaction, pre-polymerization under xenon protection after mixing The temperature of reaction is 110 DEG C, and the reaction time is 4.8 hours, and polyethylene glycol adipate two used is pure and mild when with prepolymerization reaction On the basis of the gross mass of the mixture of polytetrahydrofuran diol, the addition of the mixture of bismuth naphthenate, cobalt naphthenate and manganese acetate Amount is 420ppm, and the concentration of the mixture of the pure and mild polytetrahydrofuran diol of polyethylene glycol adipate two is in prepolymerization reaction system 66wt%；
(2) chain extending reaction；
Bis- (1H- benzimidazolyl-2 radicals-yl) ethane -1, the 2- glycol of 1,2- are added into prepolymerization reaction system, are protected in xenon Lower carry out chain extending reaction, the temperature of chain extending reaction are 118 DEG C, and the reaction time is 6.5 hours, and what is be added when being reacted gathers oneself Mixture, the 3,3 '-dimethyl -4,4 '-diphenylmethane diisocyanate of the pure and mild polytetrahydrofuran diol of naphthalate two Ester and 1, on the basis of the gross mass of bis- (1H- benzimidazolyl-2 radicals-yl) ethane -1, the 2- glycol of 2-, polyethylene glycol adipate glycol The percentage for accounting for gross mass with the mixture of polytetrahydrofuran diol is 59%, 3,3 '-dimethyl -4,4 '-diphenyl methanes two The percentage that isocyanates accounts for gross mass is 31%, and 1,2- bis- (1H- benzimidazolyl-2 radicals-yl) ethane -1,2- glycol account for gross mass Percentage be 10%, finally removed in 119 DEG C of drying and obtain within organic solvent 10 hours having benzo miaow in a kind of molecular backbone The polyurethane of oxazolyl group.
The general structure of final polyurethane obtained is as follows:
Wherein, R1ForR2ForStructure is logical In formulaPart is the soft segment of polyurethane, and soft segment is the pure and mild polytetrahydrofuran diol of polyethylene glycol adipate two Mixing segment, x=8 in general structure, n=14, the compression that polyurethane uses test method identical with embodiment 1 to measure Set value is 27%, and the hardness of polyurethane is shore 80A.
Embodiment 14
A kind of preparation method of polyurethane, comprising the following steps:
(1) prepolymerization reaction；
The mixture (mass ratio 2:1) of the polycaprolactone glycol being dehydrated and polypropylene glycol is dissolved in dimethyl sulfoxide In, 2,6- toluene di-isocyanate(TDI) and tetrabutyl titanate is then added, and progress pre-polymerization is anti-under xenon protection after mixing It answers, the temperature of prepolymerization reaction is 100 DEG C, and the reaction time is 3 hours, polycaprolactone glycol used and poly- third when with prepolymerization reaction On the basis of the gross mass of the mixture of glycol, the additive amount of tetrabutyl titanate is 500ppm, is gathered in oneself in prepolymerization reaction system The concentration of the mixture of esterdiol and polypropylene glycol is 60wt%；
(2) chain extending reaction；
Bis- (1H- benzimidazolyl-2 radicals-yl) ethane -1, the 2- glycol of 1,2- are added into prepolymerization reaction system, are protected in xenon Lower carry out chain extending reaction, the temperature of chain extending reaction are 100 DEG C, and the reaction time is 5 hours, and what is be added when being reacted gathers in oneself The mixture of esterdiol and polypropylene glycol, 2,6- toluene di-isocyanate(TDI) and bis- (1H- benzimidazolyl-2 radicals-yl) ethane -1 of 1,2-, On the basis of the gross mass of 2- glycol, the percentage that the mixture of polycaprolactone glycol and polypropylene glycol accounts for gross mass is 50%, 2, The percentage that 6- toluene di-isocyanate(TDI) accounts for gross mass is 35%, 1,2- bis- (1H- benzimidazolyl-2 radicals-yl) ethane -1,2- glycol The percentage for accounting for gross mass is 15%, finally obtains within organic solvent 10 hours band in a kind of molecular backbone in 120 DEG C of drying removals There is the polyurethane of benzimidazole group.
The general structure of final polyurethane obtained is as follows:
Wherein, R1ForR2ForIn general structurePart is the soft segment of polyurethane, and soft segment is the mixing segment of polycaprolactone glycol and polypropylene glycol, and structure is logical X=10 in formula, n=14, the compression set value that polyurethane uses test method same as Example 1 to measure for 26.8%, the hardness of polyurethane is shore 90A.
Embodiment 15-28
A kind of preparation method of polyurethane, comprising the following steps:
(1) prepolymerization reaction；
The polyester diol being dehydrated and/or polyether Glycols are dissolved in n,N-Dimethylformamide, are then added Organic diisocyanate and catalyst carry out prepolymerization reaction under nitrogen protection after mixing, and the temperature of prepolymerization reaction is 120 DEG C, the reaction time is 5 hours, on the basis of the gross mass of polyester diol and/or polyether Glycols used when prepolymerization reaction, The additive amount of catalyst is 200ppm, and polyester diol and/or the concentration of polyether Glycols are 67wt% in prepolymerization reaction system；
(2) chain extending reaction；
It is added into prepolymerization reaction system in molecular structure and has the glycol chain extender of benzimidazole group, protected in nitrogen Shield is lower to carry out chain extending reaction, and the temperature of chain extending reaction is 120 DEG C, and the reaction time is 7 hours, the polyester being added when being reacted The dihydric alcohol chain extension of benzimidazole group is had in dihydric alcohol and/or polyether Glycols, organic diisocyanate and molecular structure On the basis of the gross mass of agent, the percentage that polyester diol and/or polyether Glycols account for gross mass is 60%, organic diisocyanate The percentage that ester accounts for gross mass is 30%, and the glycol chain extender with benzimidazole group accounts for the hundred of gross mass in molecular structure Point than being 10%, is finally removed in 100 DEG C of drying and obtain within organic solvent 10 hours having benzimidazolyl in a kind of molecular backbone The polyurethane of group.
The molecular structure of the catalyst and final polyurethane obtained selected when preparation forms, repeats to tie in general structure Structure unit number, the compression set value measured using test method same as Example 1 and hardness etc. are as shown in the table.
Embodiment 29
A kind of preparation method of compound thermoplastic elastomer, includes the following steps, by styrenic thermoplastic elastomer and mine After object oil mixed on low speed, it is mixed that conjugated polyester resin, compatilizer, mineral filler, stabilizer, lubricant and polyurethane high speed is added It closes, the speed of mixed at high speed is 900rpm, and the time is 1 minute, is then added to the double screw extruder that draw ratio is greater than 36:1 In, double screw extruder, the processing temperature of double screw extruder is 190 DEG C, revolving speed 200rpm；The speed of mixed on low speed is 100rpm, time are 3 minutes；It squeezes out, is granulated and obtains thermoplastic elastomer (TPE).
Specific proportion is as follows:
The additional amount of Styrene-Butadiene-Styrene Block Copolymer (SBS) is 5 parts by weight；The weight average molecular weight of SBS It is 80,000；
The additional amount for being saturated naphthenic oil (KN4010) is 10 parts by weight；The flash-point of mineral oil is 220 DEG C；
The additional amount of TPEE is 30 parts by weight；The number-average molecular weight of conjugated polyester resin is 2000；
The additional amount of maleic anhydride-g-SBS is 1 parts by weight；
The additional amount of calcium carbonate is 10 parts by weight；The average particle size of calcium carbonate particle is 0.5nm；
The additional amount of the stabilizer (2- hydroxyl -4- zinc oxygroup benzophenone) of the functional group containing benzophenone is 1 parts by weight；
The additional amount of fatty acid ester (stearic acid) is 1 parts by weight；
The additional amount of polyurethane (polyurethane for using embodiment 5 to prepare) is 10 parts by weight；
Compound thermoplastic elastomer through above method preparation presses GB/T14522.2008 standard, ultraviolet light UV340 fluorescent tube The compression set value of product is 40% after aging 96 hours；The surface resistivity of thermoplastic elastomer (TPE) is 107Ω, compound thermal Surface resistivity after thermoplastic elastic is washed 100 times is 107Ω illustrates that antistatic property will not decay with the time；Thermoplastic Property elastomer hardness be 55A, product surface excellent effect, while there is excellent antistatic property and compression set Energy.
Embodiment 30
A kind of preparation method of compound thermoplastic elastomer, includes the following steps, by styrenic thermoplastic elastomer and mine After object oil mixed on low speed, it is mixed that conjugated polyester resin, compatilizer, mineral filler, stabilizer, lubricant and polyurethane high speed is added It closes, the speed of mixed at high speed is 1500rpm, and the time is 3 minutes, is then added to the double screw extruder that draw ratio is greater than 36:1 In, the processing temperature of double screw extruder is 250 DEG C, revolving speed 300rpm；The speed of mixed on low speed is 450rpm, and the time is 5 points Clock；It squeezes out, is granulated and obtains thermoplastic elastomer (TPE).
Specific proportion is as follows:
20 parts by weight of styrene-isoprene-styrene block copolymer (SIS)；The weight average molecular weight of SIS is 500,000；
The additional amount of saturated straight chain alkane oil (2071P) is 30 parts by weight；The flash-point of mineral oil is 260 DEG C；
The additional amount of TPEE is 50 parts by weight；The number-average molecular weight of conjugated polyester resin is 30000；
The additional amount of maleic anhydride-g-SBS is 10 parts by weight；
The additional amount of talcum powder is 35 parts by weight；The average particle size of mineral filler particle is 50nm；
The additional amount of hindered phenol stabilizer (antioxidant 1098) is 2 parts by weight；
The additional amount of fat acid amide (erucyl amide) is 2 parts by weight；
The additional amount of polyurethane (polyurethane for using embodiment 6 to prepare) is 20 parts by weight；
Compound thermoplastic elastomer through above method preparation presses GB/T14522.2008 standard, ultraviolet light UV340 fluorescent tube The compression set value of product is 45% after aging 96 hours；The surface resistivity of thermoplastic elastomer (TPE) is 108Ω, compound thermal Surface resistivity after thermoplastic elastic is washed 100 times is 108Ω illustrates that antistatic property will not decay with the time；Thermoplastic Property elastomer hardness be 85A, product surface excellent effect, while there is excellent antistatic property and compression set Energy.
Embodiment 31
A kind of preparation method of compound thermoplastic elastomer, includes the following steps, by styrenic thermoplastic elastomer and mine After object oil mixed on low speed, it is mixed that conjugated polyester resin, compatilizer, mineral filler, stabilizer, lubricant and polyurethane high speed is added It closes, the speed of mixed at high speed is 1000rpm, and the time is 2 minutes, is then added to the double screw extruder that draw ratio is greater than 36:1 In, the processing temperature of double screw extruder is 200 DEG C, revolving speed 250rpm；The speed of mixed on low speed is 300rpm, and the time is 4 points Clock；It squeezes out, is granulated and obtains thermoplastic elastomer (TPE).
Specific proportion is as follows:
The additional amount of hydrogenated styrene-butadiene-styrene block copolymers (SEBS) is 15 parts by weight；The weight of SEBS Average molecular weight is 300,000；
The additional amount for being saturated naphthenic oil (KN4006) is 20 parts by weight；The flash-point of mineral oil is 220 DEG C；
The additional amount of TPEE is 40 parts by weight；The number-average molecular weight of conjugated polyester resin is 25000；
The additional amount of maleic anhydride-g-SBS is 6 parts by weight；
The additional amount of land plaster is 20 parts by weight；The average particle size of mineral filler particle is 20nm；
The additional amount of phosphite ester stabilizer (antioxidant 626) is 1.5 parts by weight；
The additional amount of silicone (MBB50-001) is 1 parts by weight；
The additional amount of polyurethane (polyurethane for using embodiment 7 to prepare) is 15 parts by weight；
Compound thermoplastic elastomer through above method preparation presses GB/T14522.2008 standard, ultraviolet light UV340 fluorescent tube The compression set value of product is 42% after aging 96 hours；The surface resistivity of thermoplastic elastomer (TPE) is 108Ω, compound thermal Surface resistivity after thermoplastic elastic is washed 100 times is 108Ω illustrates that antistatic property will not decay with the time；Thermoplastic Property elastomer hardness be 75A, product surface excellent effect, while there is excellent antistatic property and compression set Energy.
Embodiment 32
A kind of preparation method of compound thermoplastic elastomer, includes the following steps, by styrenic thermoplastic elastomer and mine After object oil mixed on low speed, it is mixed that conjugated polyester resin, compatilizer, mineral filler, stabilizer, lubricant and polyurethane high speed is added It closes, the speed of mixed at high speed is 1200rpm, and the time is 2.5 minutes, is then added to the twin-screw extrusion that draw ratio is greater than 36:1 In machine, the processing temperature of double screw extruder is 230 DEG C, revolving speed 280rpm；The speed of mixed on low speed is 350rpm, and the time is 3.5 minute；It squeezes out, is granulated and obtains thermoplastic elastomer (TPE).
Specific proportion is as follows:
The additional amount of hydrogenated styrene isoprene-styrene block copolymer (SEPS) is 5~20 parts by weight； SEPS Weight average molecular weight be 450,000；
The additional amount of saturated straight chain alkane oil (2070P) is 15 parts by weight；The flash-point of mineral oil is 260 DEG C；
The additional amount of TPEE is 35 parts by weight；The number-average molecular weight of conjugated polyester resin is 28000；
The additional amount of maleic anhydride-g-SBS is 8 parts by weight；
The additional amount of the mixture of flake asbestos and clay is 20 parts by weight；Wherein, the mass ratio of flake asbestos and clay is 2: 1, the average particle size of mineral filler particle is 30nm；
The additional amount of (antioxidant 770) is 1 parts by weight in hindered amine stabilizer；
The additional amount of the mixture of fatty acid ester (zinc stearate) and fat acid amide (erucyl amide) is 1 parts by weight, wherein The mass ratio of zinc stearate and erucyl amide is 1:2；
The additional amount of polyurethane (polyurethane for using embodiment 8 to prepare) is 15 parts by weight；
Compound thermoplastic elastomer through above method preparation presses GB/T14522.2008 standard, ultraviolet light UV340 fluorescent tube The compression set value of product is 38% after aging 96 hours；The surface resistivity of thermoplastic elastomer (TPE) is 107Ω, compound thermal Surface resistivity after thermoplastic elastic is washed 100 times is 107Ω illustrates that antistatic property will not decay with the time；Thermoplastic Property elastomer hardness be 45A, product surface excellent effect, while there is excellent antistatic property and compression set Energy.
Embodiment 33
A kind of preparation method of compound thermoplastic elastomer, includes the following steps, by styrenic thermoplastic elastomer and mine After object oil mixed on low speed, conjugated polyester resin, compatilizer, mineral filler, stabilizer and polyurethane mixed at high speed is added, high speed is mixed The speed of conjunction is 1200rpm, and the time is 2 minutes, is then added in double screw extruder of the draw ratio greater than 36:1, double spiral shells The processing temperature of bar extruder is 220 DEG C, revolving speed 230rpm；The speed of mixed on low speed is 350rpm, and the time is 4 minutes；It squeezes out, It is granulated and obtains thermoplastic elastomer (TPE).
Specific proportion is as follows:
The additional amount of styrene ethylene-propylene-styrene block copolymer (SEEPS) is 15 parts by weight；The weight of SEEPS Average molecular weight is 300,000；
The additional amount for being saturated naphthenic oil (KN4010) is 20 parts by weight；The flash-point of mineral oil is 220 DEG C；
The additional amount of TPEE is 40 parts by weight；The number-average molecular weight of conjugated polyester resin is 26000；
The additional amount of maleic anhydride-g-SBS is 8 parts by weight；
The additional amount of barium sulfate is 18 parts by weight；The average particle size of mineral filler particle is 35nm；
The stabilizer (2- hydroxyl -4- zinc oxygroup benzophenone) and hindered phenol stabilizer (antioxygen of the functional group containing benzophenone Agent 1098) mixture additional amount be 1.5 parts by weight, wherein the stabilizer and hindered phenol stabilizer of the functional group containing benzophenone Mass ratio be 2:3；
The additional amount of polyurethane (polyurethane for using embodiment 9 to prepare) is 12 parts by weight；
Compound thermoplastic elastomer through above method preparation presses GB/T14522.2008 standard, ultraviolet light UV340 fluorescent tube The compression set value of product is 36% after aging 96 hours；The surface resistivity of thermoplastic elastomer (TPE) is 106.5Ω, it is compound Surface resistivity after thermoplastic elastomer (TPE) is washed 100 times is 106.5Ω illustrates that antistatic property will not decay with the time；Heat The hardness of thermoplastic elastic is 65A, product surface excellent effect, while having excellent antistatic property and compression set Performance.
Embodiment 34
A kind of preparation method of compound thermoplastic elastomer, includes the following steps, by styrenic thermoplastic elastomer and mine After object oil mixed on low speed, it is mixed that conjugated polyester resin, compatilizer, mineral filler, stabilizer, lubricant and polyurethane high speed is added It closes, the speed of mixed at high speed is 1500rpm, and the time is 1 minute, is then added to the double screw extruder that draw ratio is greater than 36:1 In, the processing temperature of double screw extruder is 190 DEG C, revolving speed 300rpm；The speed of mixed on low speed is 450rpm, and the time is 3 points Clock；It squeezes out, is granulated and obtains thermoplastic elastomer (TPE).
Specific proportion is as follows:
Hydrogenated styrene isoprene-styrene block copolymer (SEPS) and styrene ethylene-propylene-styrene are embedding The additional amount of section copolymer (SEEPS) mixture is 18 parts by weight, and wherein hydrogenated styrene isoprene-styrene block is total The mass ratio of polymers (SEPS) and styrene ethylene-propylene-styrene block copolymer (SEEPS) is 1:3；Hydrogenation of benzene second The weight average molecular weight of alkene-isoprene-styrene block copolymer (SEPS) is 360,000, styrene ethylene-propylene-styrene The weight average molecular weight of block copolymer (SEEPS) is 340,000；
The additional amount for being saturated naphthenic oil (KN4010) is 22 parts by weight；The flash-point of mineral oil is 220 DEG C；
The additional amount of TPEE is 42 parts by weight；The number-average molecular weight of conjugated polyester resin is 26000；
The additional amount of maleic anhydride-g-SBS is 6 parts by weight；
The additional amount of mica powder is 25 parts by weight；The average particle size of mineral filler particle is 30nm；
The additional amount of hindered amine stabilizer (antioxidant 770) is 1.6 parts by weight；
The additional amount of fatty acid ester (stearic acid) is 1.8 parts by weight；
Compound thermoplastic elastomer through above method preparation presses GB/T14522.2008 standard, ultraviolet light UV340 fluorescent tube The compression set value of product is 35% after aging 96 hours；The surface resistivity of thermoplastic elastomer (TPE) is 108Ω, compound thermal Surface resistivity after thermoplastic elastic is washed 100 times is 108Ω illustrates that antistatic property will not decay with the time；Thermoplastic Property elastomer hardness be 75A, product surface excellent effect, while there is excellent antistatic property and compression set Energy.

Claims (10)

1. a kind of compound thermoplastic elastomer, it is characterized in that: component and content are as follows:
The general structure of polyurethane is as follows:
Wherein, R1For
R2For
X is integer, and x=1-10, n are integer, n=3-15；
In general structurePart is the soft segment of polyurethane；
The compound thermoplastic elastomer presses GB/T14522.2008 standard, product after ultraviolet light UV340 fluorescent tube aging 96 hours Compression set value be 35~45%；
The surface resistivity of the compound thermoplastic elastomer is 106Ω~108Ω；The compound thermoplastic elastomer washing 100 Surface resistivity after secondary is 106Ω~108Ω。
2. compound thermoplastic elastomer according to claim 1, which is characterized in that the compound thermoplastic elastomer it is hard Degree is shore 30A~85A；The hardness range of the polyurethane is shore 80A- shore 65D；The polyurethane presses GB/ T14522.2008 standard, the compression set value of product is less than 30% after ultraviolet light UV340 fluorescent tube aging 96 hours.
3. compound thermoplastic elastomer according to claim 1, which is characterized in that the styrenic thermoplastic elastomer is Styrene block copolymer or its hydride, specially Styrene-Butadiene-Styrene Block Copolymer, styrene-isoamyl two Alkene-styrene block copolymer, hydrogenated styrene-butadiene-styrene block copolymers, hydrogenated styrene isoprene-benzene One or more of ethylene block copolymer or styrene ethylene-propylene-styrene block copolymer；The styrenic thermoplastic Property elastomer weight average molecular weight be 80,000~500,000；
The mineral oil be saturated straight chain alkane oil or be saturated naphthenic oil one or more of；The flash-point of the mineral oil is high In 150 DEG C；
The conjugated polyester resin is TPEE, and the number-average molecular weight of the conjugated polyester resin is 20000-30000；
The compatilizer is maleic anhydride-g-SBS；
The mineral filler is in calcium carbonate, talcum powder, land plaster, flake asbestos, clay, barium sulfate, mica powder or kaolin More than one, the average particle size of the mineral filler particle is 0.5~50nm；
The stabilizer is stabilizer, hindered phenol stabilizer, phosphite ester stabilizer or the hindered amine of the functional group containing benzophenone One or more of stabilizer；
The lubricant is one or more of fatty acid, fatty acid amide or silicone.
4. compound thermoplastic elastomer according to claim 1, which is characterized in that the soft segment is polyester diol chain The mixing segment of section, polyether Glycols segment or polyester diol and polyether Glycols, the polyester diol segment are to gather oneself Naphthalate segment, polyadipate -1,4- butanediol ester segment, polyadipate -1,6-HD ester segment, polyadipate Ethylene glycol -1,4- butanediol ester segment, polyadipate ethylene glycol -1,6-HD ester segment, polyadipate -1,4- butanediol - 1,6-HD ester segment, polyadipate diglycol ester segment, gathers oneself at polyadipate ethylene glycol and 1,2-propylene glycol ester segment Lactone segment, poly- carbonic acid 1,6- hexylene glycol ester segment, the polyether Glycols segment are polytetrahydrofuran segment or polypropylene glycol Segment.
5. such as the preparation method of the described in any item compound thermoplastic elastomers of Claims 1 to 4, it is characterized in that: including following Step, after styrenic thermoplastic elastomer and mineral oil mixed on low speed, be added conjugated polyester resin, compatilizer, mineral filler, Stabilizer, lubricant and polyurethane mixed at high speed, are then added to double screw extruder, squeeze out, and are granulated and obtain thermoplastic elastomehc Property body；
Polyurethane the preparation method comprises the following steps:
(1) prepolymerization reaction；
In organic solvent by the polyester diol being dehydrated and/or polyether Glycols dissolution, organic diisocyanate is then added Ester and catalyst carry out prepolymerization reaction under inert gas protection after mixing；
(2) chain extending reaction；
It is added into prepolymerization reaction system in molecular structure and has the glycol chain extender of benzimidazole group, protected in inert gas Shield is lower to carry out chain extending reaction, and then drying removal organic solvent obtains the poly- ammonia that benzimidazole group is had in a kind of molecular backbone Ester.
6. the preparation method of compound thermoplastic elastomer according to claim 5, which is characterized in that the twin-screw extrusion The processing temperature of machine is 190 DEG C~250 DEG C, revolving speed 200rpm~300rpm；The speed of the mixed on low speed be 100rpm~ 450rpm, time are 3~5 minutes；The speed of the mixed at high speed is 900rpm~1500rpm, and the time is 1~3 minute.
7. the preparation method of compound thermoplastic elastomer according to claim 5, which is characterized in that described in step (1) Polyester diol be polyethylene glycol adipate glycol, polyadipate -1,4- butyl glycol ester diol, polyadipate -1,6- oneself two Alcohol esterdiol, polyadipate ethylene glycol -1,6-HD esterdiol, gathers oneself at polyadipate ethylene glycol -1,4- butyl glycol ester diol Diacid -1,4- butanediol -1,6-HD esterdiol, polyadipate ethylene glycol and 1,2-propylene glycol esterdiol, one contracting diethyl of polyadipate Glycol esterdiol, polycaprolactone glycol or poly- carbonic acid 1,6-HD esterdiol；
The polyether Glycols are polytetrahydrofuran diol or polypropylene glycol；
The organic diisocyanate be 2,6- toluene di-isocyanate(TDI), 2,4 toluene diisocyanate, paraphenylene diisocyanate, Hexamethylene diisocyanate, diphenyl methane -4,4 '-diisocyanate, isophorone diisocyanate, phenylenedimethylidyne two are different Cyanate, 3,3 '-dimethyl -4,4 '-biphenyl diisocyanate, 4,4 '-dicyclohexyl methyl hydride diisocyanates, naphthalene -1,5- two Isocyanates or 3,3 '-dimethyl -4,4 '-methyl diphenylene diisocyanate；
The temperature of the prepolymerization reaction is 50-120 DEG C, and the reaction time is 2-5 hours；The organic solvent is N, N- dimethyl methyl Amide, DMAC N,N' dimethyl acetamide or dimethyl sulfoxide；
The catalyst be one of trimethylamine or metal organic acid salt or a variety of, wherein metal organic acid salt be bismuth, tin, Titanium, lead, zinc, potassium, antimony, cobalt, iron, nickel, molybdenum, vanadium, manganese or zirconium acylate；The inert gas be helium, neon, argon gas, Krypton or xenon；
The trimethylamine is triethylamine, triethylenediamine, N-ethylmorpholine or N, N- dimethylethanolamine；The metal has Machine hydrochlorate is bismuth neodecanoate, bismuth naphthenate, isooctyl acid bismuth, stannous octoate, dibutyl tin dilaurate, tetraisopropyl titanate, just Butyl titanate, isooctyl acid lead, zinc Isoocatanoate, zinc naphthenate, isooctyl acid potassium, potassium acetate, potassium oleate, antimony acetate, cobalt naphthenate, Nickel acetate, molybdenum naphthenate, vanadium iso-octoate or manganese acetate.
8. the preparation method of compound thermoplastic elastomer according to claim 5, which is characterized in that with prepolymerization reaction when institute On the basis of polyester diol and/or the gross mass of polyether Glycols, the additive amount of the catalyst is 15-500ppm；Institute Stating polyester diol and/or the concentration of polyether Glycols in prepolymerization reaction system is 50-67wt%.
9. the preparation method of compound thermoplastic elastomer according to claim 5, which is characterized in that described in step (2) The temperature of chain extending reaction is 80-120 DEG C, and the reaction time is 3-7 hours；The two of benzimidazole group is had in the molecular structure First alcohol chain extender is 1H- benzimidazole -5,6- glycol, 1H- benzimidazole -4,7- glycol or bis- (the 1H- benzimidazolyl-2 radicals-of 1,2- Base) ethane -1,2- glycol；The inert gas is helium, neon, argon gas, Krypton or xenon；The drying removes organic solvent Temperature be 100-120 DEG C, the time be 10-12 hours.
10. the preparation method of compound thermoplastic elastomer according to claim 5, which is characterized in that when being reacted With benzimidazole group in the polyester diol and/or polyether Glycols of addition, organic diisocyanate and molecular structure On the basis of the gross mass of glycol chain extender, polyester diol and/or polyether Glycols account for the percentage of gross mass as 40- 60%, the percentage that organic diisocyanate accounts for gross mass is 30-40%, and the binary of benzimidazole group is had in molecular structure It is arbitrary proportion when the pure and mild polyether Glycols of polyester binary are combination that it is 10-20% that alcohol chain extender, which accounts for the percentage of gross mass, Combination.
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