CN105001626A - Extrusion grade thermoplastic polyurethane elastomer and manufacturing method thereof - Google Patents
Extrusion grade thermoplastic polyurethane elastomer and manufacturing method thereof Download PDFInfo
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Abstract
The invention provides an extrusion grade thermoplastic polyurethane elastomer and a manufacturing method thereof. The extrusion grade thermoplastic polyurethane elastomer is manufactured from, by weight, 30-45 parts of polyether diol, 50-70 parts of isocyanate mixtures, 5-8.75 parts of chain extender, 5-10 parts of silicone-modified acrylic resin and 0.1-0.5 part of catalyst. The manufacturing method includes the steps that the polyether diol and the catalyst are mixed to form a mixed material A; the isocyanate mixtures and the chain extender are fused and then mixed with the mixed material A, and the formed mixture is granulated through a double-screw extruder and then cured to manufacture the extrusion grade thermoplastic polyurethane elastomer. The manufactured thermoplastic polyurethane elastomer has high mechanical properties, the tensile strength can reach over 52 MPa, the elongation can reach over 775%, the hardness range can be 60-86A, and therefore the manufactured thermoplastic polyurethane elastomer meets the industrial requirement.
Description
Technical field
The invention belongs to polyurethanes technology field, relate to a kind of polyurethane elastomer and preparation method thereof, particularly relate to a kind of wide durometer level extrusion grade Polyurethane Thermoplastic Elastomer and preparation method thereof.
Background technology
Thermoplastic polyurethane (Thermoplastic Polyurethane, TPU) a kind ofly heats melting and the macromolecular material of solvent-soluble solution.Linearly, intermolecular seldom have crosslinked TPU molecule, and second-order transition temperature is low, therefore has high strength, snappiness and excellent wear-resisting, oil resistant and low temperature tolerance characteristics.
Polyurethane termoplastic elastomer has polyester type and polyether-type two class, and the random spherical or cylindrical particle of white, relative density 1.10 ~ 1.25, polyether-type relative density is less than polyester type.The outstanding feature of polyurethane termoplastic elastomer is excellent in abrasion resistance, ozone resistance is fabulous, hardness is large, intensity is high, good springiness, low temperature resistant, have good oil resistant, chemical-resistant resistance and environmental resistance, in wet environment, polyether-type Ester hydrolysis stability far exceedes polyester type.Polyether-type thermoplastic polyurethane elastomer is the large class of one in Polyurethane Thermoplastic Elastomer, is generally synthesized by polytetramethylene ether diol (PTMGE), diphenylmethanediisocyanate (MDI) and small molecule chain extender.Compared with polyester type Polyurethane Thermoplastic Elastomer, Polyether-type thermoplastic polyurethane elastomer has excellent low-temperature performance, anti-hydrolytic performance and elasticity, obtain in film, electric wire, spandex fibre etc. and apply widely, also more and more deep to its research.
In Polyurethane Thermoplastic Elastomer, due to the uncompatibility of soft or hard section, there is obvious micro phase separation structure, wherein soft section provides elasticity mutually, and hard section plays mutually to strengthen and fills and crosslinked action.Owing to forming the ability of hydrogen bond and soft section of long-chain and the deliquescent difference of the hard section of short chain between the polar character of carbamate groups, group, cause soft or hard section thermodynamics incompatible and produce microphase-separated, between hard segment molecule, strong associations forms many microcells together and is dispersed in soft section of phase matrix.The TPU material of so final formation is not random copolymers statistically, but has the polymer chain of very high-hard section content and be almost pure soft chain segment " mixture ", and there is interactional hydrogen bond in the two-phase microcell connected at chemical bond.There is the hard section of strong polarity and hydrogen bond action in the soft segment base matter of rubbery state, play the effect of physical crosslinking point and active-reinforcing fillers.
Polyurethane Thermoplastic Elastomer has eight high-performances compared with general plastic: (1) wear resistance is strong; (2) tear strength is strong; (3) bending property is outstanding; (4) tensile strength and elongation at break high; (5) low temperature resistant-40 DEG C and high temperature resistant 150 DEG C of performances; (6) long compressive deformation rate is low; (7) oil resistant and aliphatics hydrocarbon solvent; (8) to the characteristic that oxygen and ozone have resistivity ageing-resistant.
Patent CN 1044031237A discloses a kind of extrusion grade thermoplastic polyurethane formula and preparation method thereof.This extrusion grade thermoplastic polyurethane formula is made up of the raw material of following weight part: polyester polyol 45 ~ 55 parts, diphenylmethanediisocyanate 35 ~ 45 parts, butyleneglycol 10 ~ 15 parts, antioxidant 0.2 ~ 0.5 part, environmental protection catalyst agent 0.04 ~ 0.06 part and releasing agent 0.15 ~ 0.2 part.Polyester polyol reacts obtained by hexanodioic acid and butyleneglycol in 220 DEG C of polymerization esterifications, and mass ratio is between the two 58:42.Antioxidant is the mixture of the antioxidant CHINOX618 of antioxidant CHINOX1010 and the 0.1 part of Taiwan double bond Chemical Group production that 0.1 part of Taiwan double bond Chemical Group is produced.But the durometer level of its thermoplastic polyurethane prepared is narrower, the demand to this material in existing industry can not be met; Meanwhile, its mechanical property also needs further to be improved.
Summary of the invention
For above-mentioned deficiency of the prior art, the invention provides a kind of wide durometer level extrusion grade Polyurethane Thermoplastic Elastomer and preparation method thereof.This Polyurethane Thermoplastic Elastomer not only has good mechanical property, and its durometer level can reach 50 ~ 86A, meets the requirement of the industrial width range to Polyurethane Thermoplastic Elastomer.
For reaching this object, the present invention by the following technical solutions:
First aspect, the invention provides a kind of extrusion grade Polyurethane Thermoplastic Elastomer, described Polyurethane Thermoplastic Elastomer prepares primarily of following component by weight:
Wherein, isocyanate mixture is the mixture of tolylene diisocyanate and hexamethylene vulcabond.
The weight part of above-mentioned polyether Glycols can be 30 parts, 33 parts, 35 parts, 37 parts, 40 parts, 43 parts or 45 parts etc.; The weight part of isocyanate mixture can be 50 parts, 52 parts, 54 parts, 56 parts, 58 parts, 60 parts, 62 parts, 64 parts, 66 parts, 68 parts or 70 parts etc.; The weight part of chainextender can be 5 parts, 5.3 parts, 5.5 parts, 5.7 parts, 6 parts, 6.3 parts, 6.5 parts, 6.7 parts, 7 parts, 7.3 parts, 7.5 parts, 7.7 parts, 8 parts, 8.3 parts, 8.5 parts or 8.75 parts etc.; The weight part of organosilicon modified crylic acid resin can be 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts or 10 parts etc.; The weight part of catalyzer can be 0.1 part, 0.2 part, 0.3 part, 0.4 part or 0.5 part etc.
Be preferably, described Polyurethane Thermoplastic Elastomer prepares primarily of following component by weight:
More preferably:
Organosilicon modified crylic acid resin is adopted to carry out modification as properties-correcting agent to Polyurethane Thermoplastic Elastomer in the present invention, described organosilicon modified crylic acid resin and Polyurethane Thermoplastic Elastomer are all esters polymer, the two polarity is close, there is good consistency and can good interfacial adhesion be formed, thus ensure that the physicals of material.
Preferably, described polyether Glycols is PTMG, polyoxytetramethylene glycol, the combination of any one or at least two kinds in polycyclic propylene oxide glycol or THF-PO copolymer, described combination typical case but limiting examples have: the combination of PTMG and polyoxytetramethylene glycol, the combination of polyoxytetramethylene glycol and polycyclic propylene oxide glycol, the combination of polycyclic propylene oxide glycol and THF-PO copolymer, PTMG, the combination of polyoxytetramethylene glycol and polycyclic propylene oxide glycol, PTMG, polyoxytetramethylene glycol, the combination etc. of polycyclic propylene oxide glycol and THF-PO copolymer, more preferably polyether Glycols is polyoxytetramethylene glycol.
Preferably, tolylene diisocyanate and 1 in described isocyanate mixture, the mass ratio of 6-hexylidene diisocyanate is (1 ~ 2): 1, such as 1:1,1.1:1,1.2:1,1.3:1,1.4:1,1.5:1,1.6:1,1.7:1,1.8:1,1.9:1 or 2:1 etc.; More preferably 1.5:1.
Preferably, the isocyanate index R of described isocyanate mixture is 1.02 ~ 1.1, such as 1.02,1.03,1.04,1.05,1.07,1.08,1.09 or 1.1 etc.; More preferably 1.04.
Preferably, the mass ratio of described isocyanate mixture and chainextender is (8 ~ 10): 1, such as 8:1,8.5:1,9:1,9.5:1 or 10:1 etc.
Preferably, described chainextender is the mixture of Diphenylsilanediol and ethylene glycol.
Preferably, in described chainextender, the mol ratio of Diphenylsilanediol and ethylene glycol is (2 ~ 10): 1, such as 2:1,3:1,4:1,5:1,6:1,7:1,8:1,9:1 or 10:1 etc., be preferably (3 ~ 7): 1, more preferably 4:1.
Due to, hard section in Polyurethane Thermoplastic Elastomer is made up of isocyanic ester and small molecule chain extender, and small molecule chain extender can cause speed of response to decline, and the product prepared is clamminess, crystallization difficulty and be difficult to or cannot injection molding be carried out at all, so the present invention selects the mixture of Diphenylsilanediol and ethylene glycol as chainextender, and pass through the ratio of both adjustment, the Polyurethane Thermoplastic Elastomer of production is made to have good Extrusion Flow performance, be adapted at forcing machine carries out reactive extrursion, and there is good mechanical property.Meanwhile, adopt the mixture of tolylene diisocyanate and hexamethylene vulcabond, and combination controls to belong to the R value of inventing described method, to improve the mechanical property of Polyurethane Thermoplastic Elastomer and to expand its durometer level.
Preferably, described catalyzer is stannous octoate, two (dodecyl sulphur) dibutyl tin, dibutyl tin laurate, dibutyltin diacetate, the combination of any one or at least two kinds in dialkyl tin dimaleate or triethylene diamine, described combination typical case but limiting examples have: the combination of stannous octoate and two (dodecyl sulphur) dibutyl tin, the combination of dibutyl tin laurate and dibutyltin diacetate, the combination of dialkyl tin dimaleate and triethylene diamine, stannous octoate, two (dodecyl sulphur) dibutyl tin, the combination of dibutyl tin laurate and dibutyltin diacetate, stannous octoate, two (dodecyl sulphur) dibutyl tin, dibutyl tin laurate, dibutyltin diacetate, the combination etc. of dialkyl tin dimaleate and triethylene diamine.
Second aspect, the invention provides above-mentioned method for preparing thermoplastic polyurethane elastomer, said method comprising the steps of:
(1) add in reactor by the polyether Glycols of formula ratio, control stir speed (S.S.), at 80 ~ 100 DEG C, vacuum hydro-extraction 1 ~ 3h, then adds catalyzer wherein, and supersound process makes it mix, and forms compound A;
(2) isocyanate mixture of formula ratio and chainextender being added water at 50 ~ 70 DEG C after melting adds in compound A, 30 ~ 60min is stirred at 90 ~ 110 DEG C, add again to add in twin screw extruder after organosilicon modified crylic acid resin stirs 10 ~ 30min at 90 ~ 110 DEG C and carry out extruding pelletization, obtain product B;
(3), after product B being placed 10 ~ 20h at 80 ~ 90 DEG C, Polyurethane Thermoplastic Elastomer is obtained.
Wherein, in step (1) at 80 ~ 100 DEG C vacuum hydro-extraction 1 ~ 3h, temperature can be 80 DEG C, 83 DEG C, 85 DEG C, 87 DEG C, 90 DEG C, 93 DEG C, 95 DEG C, 97 DEG C or 100 DEG C etc., and the time can be 1h, 1.5h, 2h, 2.5h or 3h etc.
Isocyanate mixture and chainextender add water melting at 50 ~ 70 DEG C in step (2), and wherein temperature can be 50 DEG C, 52 DEG C, 54 DEG C, 56 DEG C, 58 DEG C, 60 DEG C, 62 DEG C, 64 DEG C, 66 DEG C, 68 DEG C or 70 DEG C etc.; 30 ~ 60min is stirred at 90 ~ 110 DEG C, wherein temperature can be 90 DEG C, 92 DEG C, 94 DEG C, 96 DEG C, 98 DEG C, 100 DEG C, 102 DEG C, 104 DEG C, 106 DEG C, 108 DEG C or 110 DEG C etc., and churning time can be 30min, 35min, 40min, 45min, 50min, 55min or 60min etc.; Add organosilicon modified crylic acid resin and stir 10 ~ 30min at 90 ~ 110 DEG C, wherein temperature can be 90 DEG C, 92 DEG C, 94 DEG C, 96 DEG C, 98 DEG C, 100 DEG C, 102 DEG C, 104 DEG C, 106 DEG C, 108 DEG C or 110 DEG C etc., and churning time can be 10min, 15min, 20min, 25min or 30min etc.
After in step (3), product B places 10 ~ 20h at 80 ~ 90 DEG C, wherein temperature can be 80 DEG C, 81 DEG C, 82 DEG C, 83 DEG C, 84 DEG C, 85 DEG C, 86 DEG C, 87 DEG C, 88 DEG C, 89 DEG C or 90 DEG C etc., and storage period can be 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h or 20h etc.
Preferably, in step (1), stir speed (S.S.) is 1000 ~ 1500r/min, such as 1000r/min, 1050r/min, 1100r/min, 1150r/min, 1200r/min, 1250r/min, 1300r/min, 1350r/min, 1400r/min, 1450r/min or 1500r/min etc.
Preferably, in step (1), sonication treatment time is 30 ~ 60min, such as 30min, 35min, 40min, 45min, 50min, 55min or 60min etc.
Preferably, in step (2), stir speed (S.S.) is 1000 ~ 1500r/min, such as 1000r/min, 1050r/min, 1100r/min, 1150r/min, 1200r/min, 1250r/min, 1300r/min, 1350r/min, 1400r/min, 1450r/min or 1500r/min etc.
Preferably, the feeding section temperature arranging twin screw extruder in step (2) is 130 ~ 140 DEG C, such as 130 DEG C, 131 DEG C, 132 DEG C, 133 DEG C, 134 DEG C, 135 DEG C, 136 DEG C, 137 DEG C, 138 DEG C, 139 DEG C or 140 DEG C etc.
Preferably, the mixing section temperature arranging twin screw extruder in step (2) is 160 ~ 170 DEG C, such as 160 DEG C, 161 DEG C, 162 DEG C, 163 DEG C, 164 DEG C, 165 DEG C, 166 DEG C, 167 DEG C, 168 DEG C, 169 DEG C or 170 DEG C etc.
Preferably, the extruding zone temperature arranging twin screw extruder in step (2) is 170 ~ 180 DEG C, such as 170 DEG C, 171 DEG C, 172 DEG C, 173 DEG C, 174 DEG C, 175 DEG C, 176 DEG C, 177 DEG C, 178 DEG C, 179 DEG C or 180 DEG C etc.
Compared with prior art, the present invention has following beneficial effect:
The present invention adopts organosilicon modified crylic acid resin to carry out modification as properties-correcting agent to Polyurethane Thermoplastic Elastomer, described organosilicon modified crylic acid resin and Polyurethane Thermoplastic Elastomer are all esters polymer, the two polarity is close, there is good consistency and can good interfacial adhesion be formed, thus ensure that the physicals of material.Simultaneously, select the mixture of Diphenylsilanediol and ethylene glycol as chainextender, and pass through the ratio of both adjustment, the Polyurethane Thermoplastic Elastomer of production is made to have good Extrusion Flow performance, be adapted at forcing machine carries out reactive extrursion, and there is good mechanical property, make its tensile strength reach more than 52MPa, elongation reaches more than 775%.Simultaneously, adopt the mixture of tolylene diisocyanate and hexamethylene vulcabond, and combination controls to belong to the R value of inventing described method, to improve the mechanical property of Polyurethane Thermoplastic Elastomer and to expand its durometer level, its durometer level reaches 60 ~ 86A.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment only understands the present invention for helping, and should not be considered as concrete restriction of the present invention.
The mechanical property of each embodiment of the present invention and shore hardness measure by GB/T 1040-1979 and GB/T531-92 standard respectively.
Embodiment 1:
(1) taking polyoxytetramethylene glycol 37 parts adds in reactor, control stir speed (S.S.) 1300r/min, vacuum hydro-extraction 2h at 90 DEG C, then add sub-0.3 part, the tin of octoate catalyst wherein, supersound process 45min makes it mix, and forms compound A;
(2) (wherein, in isocyanate mixture, the mass ratio of tolylene diisocyanate and hexamethylene vulcabond is 1.5:1 to take isocyanate mixture 60 parts; And R is 1.04) and chainextender 6 parts is (wherein, the mol ratio of Diphenylsilanediol and ethylene glycol is 4:1) add in compound A after the melting that adds water at 60 DEG C, 50min is stirred at 100 DEG C, add in twin screw extruder after stirring 15min at adding organosilicon modified crylic acid resin 7 parts in 100 DEG C again and carry out extruding pelletization, obtain product B;
Wherein, the feeding section temperature arranging twin screw extruder is 135 DEG C, and mixing section temperature is 165 DEG C, and extruding zone temperature is 175 DEG C.
(3), after product B being placed 15h at 85 DEG C, Polyurethane Thermoplastic Elastomer is obtained.
Carry out performance test to obtained Polyurethane Thermoplastic Elastomer, test result is listed in table 1.
Embodiment 2:
(1) taking polycyclic propylene oxide glycol 40 parts adds in reactor, control stir speed (S.S.) 1000r/min, vacuum hydro-extraction 3h at 80 DEG C, then add catalyst dibutyltin dilaurylate 0.2 part wherein, supersound process 60min makes it mix, and forms compound A;
(2) (wherein, in isocyanate mixture, the mass ratio of tolylene diisocyanate and hexamethylene vulcabond is 1:1 to take isocyanate mixture 65 parts; And R is 1.02) and chainextender 8.125 parts is (wherein, the mol ratio of Diphenylsilanediol and ethylene glycol is 3:1) add in compound A after the melting that adds water at 50 DEG C, 60min is stirred at 90 DEG C, add in twin screw extruder after stirring 30min at adding organosilicon modified crylic acid resin 8 parts in 90 DEG C again and carry out extruding pelletization, obtain product B;
Wherein, the feeding section temperature arranging twin screw extruder is 130 DEG C, and mixing section temperature is 160 DEG C, and extruding zone temperature is 170 DEG C.
(3), after product B being placed 20h at 80 DEG C, Polyurethane Thermoplastic Elastomer is obtained.
Carry out performance test to obtained Polyurethane Thermoplastic Elastomer, test result is listed in table 1.
Embodiment 3:
(1) taking polycyclic propylene oxide glycol 35 parts adds in reactor, control stir speed (S.S.) 1500r/min, vacuum hydro-extraction 1h at 100 DEG C, then two (dodecyl sulphur) dibutyl tin 0.4 part of catalyzer is added wherein, supersound process 30min makes it mix, and forms compound A;
(2) (wherein, in isocyanate mixture, the mass ratio of tolylene diisocyanate and hexamethylene vulcabond is 2:1 to take isocyanate mixture 55 parts; And R is 1.1) and chainextender 5.5 parts is (wherein, the mol ratio of Diphenylsilanediol and ethylene glycol is 7:1) add in compound A after the melting that adds water at 70 DEG C, 30min is stirred at 110 DEG C, add in twin screw extruder after stirring 10min at adding organosilicon modified crylic acid resin 6 parts in 110 DEG C again and carry out extruding pelletization, obtain product B;
Wherein, the feeding section temperature arranging twin screw extruder is 140 DEG C, and mixing section temperature is 170 DEG C, and extruding zone temperature is 180 DEG C.
(3), after product B being placed 10h at 90 DEG C, Polyurethane Thermoplastic Elastomer is obtained.
Carry out performance test to obtained Polyurethane Thermoplastic Elastomer, test result is listed in table 1.
Embodiment 4:
Except taking PTMG 45 parts, catalyzer dialkyl tin dimaleate 0.1 part, isocyanate mixture 70 parts and chainextender 8.75 parts (wherein by weight, the mol ratio of Diphenylsilanediol and ethylene glycol is 10:1) and organosilicon modified crylic acid resin 10 is especially, other steps are all in the same manner as in Example 1.
Carry out performance test to obtained Polyurethane Thermoplastic Elastomer, test result is listed in table 1.
Embodiment 5:
Except taking polyoxytetramethylene glycol 30 parts, catalyzer dialkyl tin dimaleate 0.5 part, isocyanate mixture 50 parts and chainextender 5 parts (wherein by weight, the mol ratio of Diphenylsilanediol and ethylene glycol is 2:1) and organosilicon modified crylic acid resin 5 is especially, other steps are all in the same manner as in Example 1.
Carry out performance test to obtained Polyurethane Thermoplastic Elastomer, test result is listed in table 1.
Comparative example 1:
Except not adopting organosilicon modified crylic acid resin to carry out except modification to Polyurethane Thermoplastic Elastomer, other steps are all in the same manner as in Example 1.
Carry out performance test to obtained Polyurethane Thermoplastic Elastomer, test result is listed in table 1.
Comparative example 2:
Except isocyanic ester is tolylene diisocyanate, other steps are all in the same manner as in Example 1.
Carry out performance test to obtained Polyurethane Thermoplastic Elastomer, test result is listed in table 1.
Comparative example 3:
Except isocyanic ester is hexamethylene vulcabond, other steps are all in the same manner as in Example 1.
Carry out performance test to obtained Polyurethane Thermoplastic Elastomer, test result is listed in table 1.
Comparative example 4:
Isocyanate index R except isocyanate mixture is except 0.9, and other steps are all in the same manner as in Example 1.
Carry out performance test to obtained Polyurethane Thermoplastic Elastomer, test result is listed in table 1.
Comparative example 5:
Isocyanate index R except isocyanate mixture is except 1.4, and other steps are all in the same manner as in Example 1.
Carry out performance test to obtained Polyurethane Thermoplastic Elastomer, test result is listed in table 1.
Comparative example 6:
Except chainextender is Diphenylsilanediol, other steps are all in the same manner as in Example 1.
Carry out performance test to obtained Polyurethane Thermoplastic Elastomer, test result is listed in table 1.
Comparative example 7:
Except chainextender is ethylene glycol, other steps are all in the same manner as in Example 1.
Carry out performance test to obtained Polyurethane Thermoplastic Elastomer, test result is listed in table 1.
Comparative example 8:
Except each substances content and ratio adopt the extraneous data described in the present invention, other steps are all in the same manner as in Example 1.
Carry out performance test to obtained Polyurethane Thermoplastic Elastomer, test result is listed in table 1.
Polyurethane Thermoplastic Elastomer performance test table prepared by table 1: embodiment 1-5 and comparative example 1-8
Polyurethane Thermoplastic Elastomer the performance test results prepared by integrated embodiment 1-5 and comparative example 1-8 can be found out, organosilicon modified crylic acid resin is adopted to carry out modification as properties-correcting agent to Polyurethane Thermoplastic Elastomer, described organosilicon modified crylic acid resin and Polyurethane Thermoplastic Elastomer are all esters polymer, the two polarity is close, there is good consistency and can good interfacial adhesion be formed, thus ensure that the physicals of material.Simultaneously, select the mixture of Diphenylsilanediol and ethylene glycol as chainextender, and pass through the ratio of both adjustment, the Polyurethane Thermoplastic Elastomer of production is made to have good Extrusion Flow performance, be adapted at forcing machine carries out reactive extrursion, and there is good mechanical property, make its tensile strength reach more than 52MPa, elongation reaches more than 775%.Simultaneously, adopt the mixture of tolylene diisocyanate and hexamethylene vulcabond, and combination controls to belong to the R value of inventing described method, to improve the mechanical property of Polyurethane Thermoplastic Elastomer and to expand its durometer level, its durometer level reaches 60 ~ 86A.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. an extrusion grade Polyurethane Thermoplastic Elastomer, is characterized in that, described Polyurethane Thermoplastic Elastomer prepares primarily of following component by weight:
Wherein, isocyanate mixture is the mixture of tolylene diisocyanate and hexamethylene vulcabond.
2. Polyurethane Thermoplastic Elastomer according to claim 1, is characterized in that, described Polyurethane Thermoplastic Elastomer prepares primarily of following component by weight:
More preferably:
3. Polyurethane Thermoplastic Elastomer according to claim 1 and 2, it is characterized in that, described polyether Glycols is the combination of any one or at least two kinds in PTMG, polyoxytetramethylene glycol, polycyclic propylene oxide glycol or THF-PO copolymer;
Preferably, described polyether Glycols is polyoxytetramethylene glycol.
4. the Polyurethane Thermoplastic Elastomer according to any one of claim 1-3, is characterized in that, in described isocyanate mixture, the mass ratio of tolylene diisocyanate and hexamethylene vulcabond is (1 ~ 2): 1;
Preferably, in described isocyanate mixture, the mass ratio of tolylene diisocyanate and hexamethylene vulcabond is 1.5:1;
Preferably, the isocyanate index R of described isocyanate mixture is 1.02 ~ 1.1;
Preferably, the isocyanate index R of described isocyanate mixture is 1.04.
5. the Polyurethane Thermoplastic Elastomer according to any one of claim 1-4, is characterized in that, the mass ratio of described isocyanate mixture and chainextender is (8 ~ 10): 1;
Preferably, described chainextender is the mixture of Diphenylsilanediol and ethylene glycol;
Preferably, in described chainextender, the mol ratio of Diphenylsilanediol and ethylene glycol is (2 ~ 10): 1;
Preferably, in described chainextender, the mol ratio of Diphenylsilanediol and ethylene glycol is (3 ~ 7): 1;
Preferably, in described chainextender, the mol ratio of Diphenylsilanediol and ethylene glycol is 4:1;
Preferably, described catalyzer is the combination of any one or at least two kinds in stannous octoate, two (dodecyl sulphur) dibutyl tin, dibutyl tin laurate, dibutyltin diacetate, dialkyl tin dimaleate or triethylene diamine.
6. the method for preparing thermoplastic polyurethane elastomer according to any one of claim 1-5, is characterized in that, said method comprising the steps of:
(1) add in reactor by the polyether Glycols of formula ratio, control stir speed (S.S.), at 80 ~ 100 DEG C, vacuum hydro-extraction 1 ~ 3h, then adds catalyzer wherein, and supersound process makes it mix, and forms compound A;
(2) isocyanate mixture of formula ratio and chainextender being added water at 50 ~ 70 DEG C after melting adds in compound A, 30 ~ 60min is stirred at 90 ~ 110 DEG C, add again to add in twin screw extruder after organosilicon modified crylic acid resin stirs 10 ~ 30min at 90 ~ 110 DEG C and carry out extruding pelletization, obtain product B;
(3), after product B being placed 10 ~ 20h at 80 ~ 90 DEG C, Polyurethane Thermoplastic Elastomer is obtained.
7. method for preparing thermoplastic polyurethane elastomer according to claim 6, is characterized in that, in step (1), stir speed (S.S.) is 1000 ~ 1500r/min;
Preferably, in step (1), sonication treatment time is 30 ~ 60min.
8. the method for preparing thermoplastic polyurethane elastomer according to claim 6 or 7, is characterized in that, in step (2), stir speed (S.S.) is 1000 ~ 1500r/min.
9. the method for preparing thermoplastic polyurethane elastomer according to any one of claim 6-8, is characterized in that, the feeding section temperature arranging twin screw extruder in step (2) is 130 ~ 140 DEG C.
10. the method for preparing thermoplastic polyurethane elastomer according to any one of claim 6-9, is characterized in that, the mixing section temperature arranging twin screw extruder in step (2) is 160 ~ 170 DEG C;
Preferably, the extruding zone temperature arranging twin screw extruder in step (2) is 170 ~ 180 DEG C.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105860508A (en) * | 2016-06-08 | 2016-08-17 | 东莞市吉鑫高分子科技有限公司 | Rolling-grade thermoplastic polyurethane elastomer and preparing method thereof |
| CN106008898A (en) * | 2016-07-28 | 2016-10-12 | 东莞市吉鑫高分子科技有限公司 | High-moisture-resistance cold/heat-resistant thermoplastic polyurethane elastomer and preparation method thereof |
| CN107141441A (en) * | 2017-06-02 | 2017-09-08 | 东莞市吉鑫高分子科技有限公司 | A kind of low-refraction high transparency TPUE and preparation method thereof |
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| EP3838945A1 (en) | 2019-12-17 | 2021-06-23 | Covestro Deutschland AG | Thermoplastic aliphatic polyurethane prepolymer with improved melting behaviour |
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| EP3838946A1 (en) | 2019-12-17 | 2021-06-23 | Covestro Deutschland AG | Method for producing a low colour thermoplastic polyurethane |
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| CN105860508A (en) * | 2016-06-08 | 2016-08-17 | 东莞市吉鑫高分子科技有限公司 | Rolling-grade thermoplastic polyurethane elastomer and preparing method thereof |
| CN106008898A (en) * | 2016-07-28 | 2016-10-12 | 东莞市吉鑫高分子科技有限公司 | High-moisture-resistance cold/heat-resistant thermoplastic polyurethane elastomer and preparation method thereof |
| CN107141441A (en) * | 2017-06-02 | 2017-09-08 | 东莞市吉鑫高分子科技有限公司 | A kind of low-refraction high transparency TPUE and preparation method thereof |
| CN108034224A (en) * | 2017-12-19 | 2018-05-15 | 滁州环球聚氨酯科技有限公司 | A kind of surface coated layer of polyurethane preparation method of forklift hub |
| CN108017900A (en) * | 2017-12-22 | 2018-05-11 | 广州机械科学研究院有限公司 | A kind of hydropneumatic sealing self-lubricating thermoplastic polyurethane elastomer material and its preparation method and application |
| EP3838949A1 (en) | 2019-12-17 | 2021-06-23 | Covestro Deutschland AG | Method for the continuous production of a thermoplastic polyurethane |
| EP3838533A1 (en) | 2019-12-17 | 2021-06-23 | Covestro Deutschland AG | Reactive extrusion of tpu with degassing |
| EP3838945A1 (en) | 2019-12-17 | 2021-06-23 | Covestro Deutschland AG | Thermoplastic aliphatic polyurethane prepolymer with improved melting behaviour |
| EP3838396A1 (en) | 2019-12-17 | 2021-06-23 | Covestro Deutschland AG | Reactive extrusion of tpu using water |
| EP3838955A1 (en) | 2019-12-17 | 2021-06-23 | Covestro Deutschland AG | Method for producing thermoplastic polyurethane having low melting enthalpy |
| EP3838946A1 (en) | 2019-12-17 | 2021-06-23 | Covestro Deutschland AG | Method for producing a low colour thermoplastic polyurethane |
| WO2021122300A1 (en) | 2019-12-17 | 2021-06-24 | Covestro Intellectual Property Gmbh & Co. Kg | Method for producing a thermoplastic polyurethane with low melt enthalpy |
| WO2021122307A1 (en) | 2019-12-17 | 2021-06-24 | Covestro Intellectual Property Gmbh & Co. Kg | Method for continuously producing a thermoplastic polyurethane |
| WO2021122283A1 (en) | 2019-12-17 | 2021-06-24 | Covestro Intellectual Property Gmbh & Co. Kg | Reactive extrusion of tpu with degassing process |
| WO2021122309A1 (en) | 2019-12-17 | 2021-06-24 | Covestro Intellectual Property Gmbh & Co. Kg | Method for producing a thermoplastic polyurethane with a low colour number |
| WO2021122282A1 (en) | 2019-12-17 | 2021-06-24 | Covestro Intellectual Property Gmbh & Co. Kg | Reactive extrusion of tpu while supplying water |
| WO2021122305A1 (en) | 2019-12-17 | 2021-06-24 | Covestro Intellectual Property Gmbh & Co. Kg | Thermoplastic aliphatic polyurethane polymer having an improved melting behavior |
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