CN103965614B - A kind of rapid shaping method for preparing thermoplastic polyurethane elastomer - Google Patents
A kind of rapid shaping method for preparing thermoplastic polyurethane elastomer Download PDFInfo
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- CN103965614B CN103965614B CN201410216307.5A CN201410216307A CN103965614B CN 103965614 B CN103965614 B CN 103965614B CN 201410216307 A CN201410216307 A CN 201410216307A CN 103965614 B CN103965614 B CN 103965614B
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- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 36
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 36
- 238000007493 shaping process Methods 0.000 title claims abstract description 24
- 229920001971 elastomer Polymers 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000000806 elastomer Substances 0.000 title claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 30
- 239000000314 lubricant Substances 0.000 claims abstract description 27
- 229920002635 polyurethane Polymers 0.000 claims abstract description 24
- 239000004814 polyurethane Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000002844 melting Methods 0.000 claims abstract description 22
- 230000008018 melting Effects 0.000 claims abstract description 22
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 21
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 239000003112 inhibitor Substances 0.000 claims abstract description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 239000004970 Chain extender Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 230000018044 dehydration Effects 0.000 claims description 14
- 238000006297 dehydration reaction Methods 0.000 claims description 14
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 150000002191 fatty alcohols Chemical class 0.000 claims description 12
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 7
- 125000005907 alkyl ester group Chemical group 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 125000003827 glycol group Chemical group 0.000 claims description 4
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 3
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- VQPKAMAVKYTPLB-UHFFFAOYSA-N lead;octanoic acid Chemical compound [Pb].CCCCCCCC(O)=O VQPKAMAVKYTPLB-UHFFFAOYSA-N 0.000 claims description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 6
- 238000001746 injection moulding Methods 0.000 abstract description 4
- 229920003225 polyurethane elastomer Polymers 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 150000003384 small molecules Chemical group 0.000 abstract 1
- 238000009826 distribution Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 6
- 239000002826 coolant Substances 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- 150000003077 polyols Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- ICLCCFKUSALICQ-UHFFFAOYSA-N 1-isocyanato-4-(4-isocyanato-3-methylphenyl)-2-methylbenzene Chemical compound C1=C(N=C=O)C(C)=CC(C=2C=C(C)C(N=C=O)=CC=2)=C1 ICLCCFKUSALICQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
The invention discloses a kind of rapid shaping method for preparing thermoplastic polyurethane elastomer: 1) compound molecule lubricant is used special efficient mixing machine mixing for standby use; 2) polyester polyol, oxidation inhibitor, catalyzer are added melting mixing in reactor and dewater for subsequent use; 3) the mixing section ratio of twin screw extruder is increased to 35% by 25%, reduces conversion zone thread pitch 4 ~ 14% simultaneously.Polyester polyol, small molecule chain extender, vulcabond three components are filled in twin screw extruder respectively by high precision gear wheel pump and carry out reaction mixing, simultaneously after compound molecule lubricant to add to and mixes with polyurethane elastomer melt in twin screw extruder by twin screw extruder middle portion, obtain the Polyurethane Thermoplastic Elastomer particle of rapid shaping through underwater cutpellet.The rapid shaping Polyurethane Thermoplastic Elastomer that preparation method of the present invention obtains has hardened forming speed, more excellent mechanical property faster when injection molding.
Description
Technical field
The present invention relates to a kind of method for preparing thermoplastic polyurethane elastomer, particularly relate to rapid shaping method for preparing thermoplastic polyurethane elastomer.
Background technology
Snap cure molded thermoplastic polyurethane elastomer material is widely used in general-purpose injection part material as goods such as loom polyurethane rubber wheel, polyurethane plate, rubber rolls, because Polyurethane Thermoplastic Elastomer (TPU) is when injection molding, the speed of its hardened forming speed is important index, hardened forming speed can improve the output capacity of goods faster, thus reduce production cost and save energy, and the molding time >=45S of general injection molding thermoplastic polyurethane material, can not meet the requirement of client to output capacity.
Summary of the invention
Technical problem to be solved by this invention, provides a kind of hardened forming injection-type macromolecule polyurethane method for producing elastomers faster, makes the molding time of product be down to 35S from traditional 45S.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is: a kind of rapid shaping method for preparing thermoplastic polyurethane elastomer, the steps include:
1) polyester polyol is added reactor after 90 ~ 200 DEG C of meltings, then add oxidation inhibitor, catalyzer; Keep reactor temperature at 90 ~ 200 DEG C, adjustment reacting kettle inner pressure is to-0.08 ~-0.1MPa, and dehydration 0.5 ~ 8h, is then cooled to 75 ~ 115 DEG C, passes into nitrogen and removes vacuum, form component A;
Described oxidation inhibitor accounts for 2 ~ 10 ‰ of polyester polyol total mass, and described catalyzer accounts for 70 ~ 600ppm of polyester polyol total mass;
2) vulcabond is heated to 40 ~ 140 DEG C of meltings, forms component B;
3) glycol chain extender is heated to 30 ~ 120 DEG C, after complete melting, adjustment reactor pressure-0.08 ~-0.1MPa, dehydration 4 ~ 6h, forms component C;
4) carbonatoms is more than or equal to the higher aliphatic alkane of 16, high fatty alcohol that carbonatoms is more than or equal to 16 in mass ratio 5:1 ~ 1:1 mix, add alkyl esters lubricant again, mix with special efficient mixing machine, obtain compound molecule lubricant;
Carbonatoms after mixing is more than or equal to the higher aliphatic alkane of 16 and the mass ratio of the carbonatoms amount of the mixture and alkyl esters lubricant that are more than or equal to the high fatty alcohol of 16 is 1:1 ~ 1:5;
5) adjustment of the mixing section ratio of forcing machine is increased to 25 ~ 35%, conversion zone threaded block pitch is reduced by 30 ~ 45%;
Account for 21% of screw rod total length before described forcing machine mixing section ratio adjustment, before the adjustment of conversion zone screw thread ratio, account for 79% of screw rod total length;
Described threaded block pitch refers to the pitch of twin screw thread segment, reduces pitch and can reduce the single cavity volume be made up of screw thread; Described mixing section refers to the part be made up of mixing spiral shell block;
6) by component A, component B, component C in mass ratio 45:13:42 ~ 65:8:27 pour into (three components are provided with high-efficiency turbine mixing device at perfusing hole place) in twin screw extruder simultaneously, step-reaction polymerization obtains Polyurethane Thermoplastic Elastomer (TPU), at the middle part of twin screw extruder by step 4) the compound molecule lubricant for preparing is added in twin screw extruder and fully mixes in an extruder with Polyurethane Thermoplastic Elastomer (TPU), obtains rapid shaping Polyurethane Thermoplastic Elastomer.
Described component A, component B, component C high class gear volume pump are metered into, volume pump error < ± 0.5 ‰; Described compounded lubricant is metered into by high precision Weightlessness balance, Weightlessness balance error < ± 0.5%.
The addition of described compound molecule lubricant accounts for 2 ‰ ~ 10 ‰ of component A, component B and component C three total mass.
Described polyester polyol is obtained through polycondensation by di-carboxylic acid and dibasic alcohol, and the number-average molecular weight of polyester polyol is 1000 ~ 6000.
Described di-carboxylic acid is aliphatic dicarboxylic acid or aromatic binary carboxylic acid; Described dibasic alcohol is selected from one or more in following substances: ethylene glycol, BDO, 1,6-hexylene glycol, 2，2-dimethyl-1，3-propanediol.
Described vulcabond acid esters is selected from 4,4 ＇-diphenylmethanediisocyanate (MDI), naphthalene diisocyanate (1,5-NDI), PPDI (PPDI), 4,4 ＇-dicyclohexyl methane diisocyanate (H12MDI), 3,3 ＇-dimethyl diphenyl-4, one or both and above mixture in 4 ＇-vulcabond (TODI), 3,3 ＇-dimethyl-4,4 ＇-diphenylmethanediisocyanate.
Described glycol chain extender be C4 ~ C8 straight diol, containing the symmetry of phenyl ring or asymmetrical two terminal hydroxy group things.
The higher aliphatic alkane that described carbonatoms is more than or equal to 16 is the higher aliphatic straight-chain paraffin of C16 ~ C36.The high fatty alcohol that described carbonatoms is more than or equal to 16 is the higher aliphatic straight chain alcohol of C16 ~ C36.
Described alkyl esters lubricant is the monoesters that the aliphatic saturated monocarboxylic acid of C8 ~ C16 and the straight chain alcohol of C4 ~ C8 are formed.
Described oxidation inhibitor is selected from one or both and above mixture in antioxidant 1010, antioxidant 1076, irgasfos 168, oxidation inhibitor 626, oxidation inhibitor 245.
Described catalyzer is selected from one or both and above mixture in stannous octoate, dibutyl tin dilaurate, lead octoate 36, two acetic acid di-n-butyl tins.
Beneficial effect of the present invention: the rapid shaping Polyurethane Thermoplastic Elastomer adopting preparation method of the present invention to obtain has hardened forming speed, more excellent mechanical property faster when injection molding, concrete principle is as follows:
1) utilisation technology of compound molecule lubricant: compound molecule lubricant overcomes the TPU defect that TPU molecule is not easily wriggled when hardening crystalline forming, composite by introducing higher aliphatic alkane, high fatty alcohol and lower alkyl ester class, gap lubrication (especially can reduce the efficiency that hard section and soft period of initial stage form hydrogen bond) is played to macromole TPU, TPU hard segment and soft chain segment can be wriggled to crystallization position simultaneously fast, accelerate hardened forming;
2) molecular weight of synthesis of polyurethane and molecular weight distribution control techniques: the number-average molecular weight of the equivalents ratio control TPU of-NCO/-OH in adjustment synthesis TPU formula.
3) the adjustment utilisation technology of twin screw extruder chamber of the reactor: by the screw thread configuration of adjustment reactor twin screw extruder, mixing section ratio is increased, the ratio of suitable reduction reaction chamber, and reduce single cavity volume to improve the mixing efficiency in reaction process, thus control synthesis time TPU molecular weight distribution width.
The key technical indexes of the rapid shaping Polyurethane Thermoplastic Elastomer obtained by the present invention: molecular weight distribution width (DMW): <2; Number-average molecular weight (Mn): 30000-50000; Standard 25 DEG C of water coolant hardened forming time: <35S; Tensile strength: 25-35MPa; Elongation: 500-700%; Tear strength: 60-88KN/m.
Tensile strength, unit elongation, tear strength measuring method: ISO37-2005; Molecular weight distribution width and number-average molecular weight measuring method: gel chromatography.
Embodiment
Specific embodiment of the invention scheme is described below in detail.
Example 1
The antioxidant 1010 accounting for polyester polyol quality 6 ‰ is added in reactor, account for the stannous octoate of polyester polyol quality 200ppm, by hexanodioic acid and 1, the equal molecular mass of number of 4-butyleneglycol condensation is the polyester polyol of 2500, test tank is put into after dehydration melting mixing 5h under 95 DEG C of temperature condition and-0.08 ~-0.1MPa vacuum tightness, open test tank stir and stop vacuum and inflated with nitrogen after being evacuated to-0.085MPa, form component A for subsequent use;
By diphenylmethanediisocyanate 43.5 DEG C of meltings and vacuum is drawn in test tank, formed in component B for subsequent use;
By BDO 40 DEG C of meltings, and vacuum is drawn in test tank, and-0.08 ~-0.1MPa vacuum tightness dehydration 4h, forms component C for subsequent use;
After 2:1:6 high efficient mixer mixes in mass ratio by the higher aliphatic alkane of C22, the high fatty alcohol of C36 and sad mono—n—butylester, obtain compound molecule lubricant;
By component A, component B, component C is respectively by high class gear volume pump 50:12:38[formulating of recipe R (ratio of NCO/OH) value=0.995 in mass ratio] to be filled into mixing section ratio be 25% simultaneously, conversion zone pitch reduces in the twin screw extruder of 4% (conversion zone screw thread ratio accounts for 75% of total screw rod), setting forcing machine rotating speed is 250RPM, setting 1# ~ 6# temperature is 110 DEG C ~ 160 DEG C, 7# ~ 12# temperature is reaction mixing under the condition of 195 DEG C ~ 170 DEG C, 7# by high precision Weightlessness balance compound molecule lubricant to be added into by 5 ‰ of Polyurethane Thermoplastic Elastomer (TPU) total amount mix with TPU melt in forcing machine after obtain rapid shaping Polyurethane Thermoplastic Elastomer particle through underwater cutpellet.
The key technical indexes: molecular weight distribution width (DMW): <2; Number-average molecular weight (Mn): 32000; Standard 25 DEG C of water coolant hardened forming time: <32S; Tensile strength: 33MPa; Elongation: 580%; Tear strength: 68KN/m
Embodiment 2
The antioxidant 1010 accounting for polyester polyol quality 6 ‰ is added in reactor, account for the stannous octoate of polyester polyol quality 200ppm, by hexanodioic acid and 1, the equal molecular mass of number of 4-butyleneglycol condensation is the polyester polyol of 2500, be put in test tank after dehydration melting mixing 5h under 95 DEG C of temperature condition and-0.08 ~-0.1MPa vacuum tightness, open test tank stir and stop vacuum and inflated with nitrogen after being evacuated to-0.085MPa, component A is for subsequent use;
By diphenylmethanediisocyanate 43.5 DEG C of meltings and vacuum is drawn into test tank, component B is for subsequent use;
By BDO 40 DEG C of meltings and vacuum is drawn in test tank ,-0.08 ~-0.1MPa vacuum tightness dehydration 4h, forms component C for subsequent use;
By the higher aliphatic alkane of C22, the high fatty alcohol of C36 and sad mono—n—butylester in mass ratio 2:1:6 high efficient mixer mix, obtain compound molecule lubricant;
By component A, component B, component C is by high class gear volume pump 50:12:38[formulating of recipe R (ratio of NCO/OH) value=1.005 in mass ratio] to be filled into mixing section ratio be 30% simultaneously, conversion zone pitch reduces in the twin screw extruder of 9% (conversion zone screw thread ratio accounts for 70% of total screw rod), setting forcing machine rotating speed is 250RPM, setting 1# ~ 6# temperature is 110 DEG C ~ 160 DEG C, 7# ~ 12# temperature is reaction mixing under the condition of 195 DEG C ~ 170 DEG C, 7# by high precision Weightlessness balance compound molecule lubricant to be added into by 8 ‰ of Polyurethane Thermoplastic Elastomer (TPU) total amount mix with TPU melt in forcing machine after obtain rapid shaping Polyurethane Thermoplastic Elastomer particle through underwater cutpellet.
The key technical indexes: molecular weight distribution width (DMW): <2; Number-average molecular weight (Mn): 39000; Standard 25 DEG C of water coolant hardened forming time: <33S; Tensile strength: 36MPa; Elongation: 520%; Tear strength: 70KN/m
Embodiment 3
The antioxidant 1010 accounting for polyol quality 6 ‰ is added in reactor, account for the stannous octoate of polyol quality 200ppm, by hexanodioic acid and 1, the equal molecular mass of number of 4-butyleneglycol condensation is the polyester polyol of 2500, be put in test tank after dehydration melting mixing 5h under 95 DEG C of temperature condition and-0.08 ~-0.1MPa vacuum tightness, open test tank stir and stop vacuum and inflated with nitrogen after being evacuated to-0.085MPa, form component A for subsequent use;
By diphenylmethanediisocyanate 43.5 DEG C of meltings and vacuum is drawn in test tank, form component B for subsequent use;
By BDO 40 DEG C of meltings and vacuum is drawn in test tank ,-0.08 ~-0.1MPa vacuum tightness dehydration 4h, forms component C for subsequent use;
After 2:1:6 high efficient mixer mixes in mass ratio by the higher aliphatic alkane of C22, the high fatty alcohol of C36 and sad mono—n—butylester, obtain compound molecule lubricant;
By component A, component B, component C is by high class gear volume pump 50:12:38[formulating of recipe R (ratio of NCO/OH) value=1.01 in mass ratio] to be filled into mixing section ratio be 30% simultaneously, conversion zone pitch reduces in the twin screw extruder of 9% (conversion zone screw thread ratio accounts for 70% of total screw rod), setting forcing machine rotating speed is 250RPM, setting 1# ~ 6# temperature is 110 DEG C ~ 160 DEG C, 7# ~ 12# temperature is reaction mixing under the condition of 195 DEG C ~ 170 DEG C, 7# by high precision Weightlessness balance compound molecule lubricant to be added into by 5 ‰ of Polyurethane Thermoplastic Elastomer (TPU) total amount mix with TPU melt in forcing machine after obtain rapid shaping Polyurethane Thermoplastic Elastomer particle through underwater cutpellet.
The key technical indexes: molecular weight distribution width (DMW): <2; Number-average molecular weight (Mn): 43000; Standard 25 DEG C of water coolant hardened forming time: <35S; Tensile strength: 43MPa; Elongation: 680%; Tear strength: 82KN/m
Embodiment 4
The antioxidant 1010 accounting for polyol quality 6 ‰ will be added in reactor, account for the stannous octoate of polyol quality 200ppm, same by hexanodioic acid and 1, the equal molecular mass of number of 4-butyleneglycol condensation is the polyester polyol of 2500, be put in test tank after dehydration melting mixing 5h under 95 DEG C of temperature condition and-0.08 ~-0.1MPa vacuum tightness, open test tank stir and stop vacuum and inflated with nitrogen after being evacuated to-0.085MPa, form component A for subsequent use;
By diphenylmethanediisocyanate 43.5 DEG C of meltings and vacuum is drawn in test tank, form component B for subsequent use;
By BDO 40 DEG C of meltings and vacuum is drawn in test tank ,-0.08 ~-0.1MPa vacuum tightness dehydration 4h, forms component C for subsequent use;
By the higher aliphatic alkane of C22, the high fatty alcohol of C36 and sad mono—n—butylester in mass ratio 2:1:6 high efficient mixer mix, obtain compound molecule lubricant;
By component A, component B, component C is by high class gear volume pump 50:12:38[formulating of recipe R (ratio of NCO/OH) value=1.015 in mass ratio] to be filled into mixing section ratio be 35% simultaneously, conversion zone pitch reduces in the twin screw extruder of 14% (conversion zone screw thread ratio accounts for 65% of total screw rod), setting forcing machine rotating speed is 250RPM, setting 1# ~ 6# temperature is 110 DEG C ~ 160 DEG C, 7# ~ 12# temperature is reaction mixing under the condition of 195 DEG C ~ 170 DEG C, 7# by high precision Weightlessness balance compound molecule lubricant to be added into by 5 ‰ of Polyurethane Thermoplastic Elastomer (TPU) total amount mix with TPU melt in forcing machine after obtain rapid shaping Polyurethane Thermoplastic Elastomer particle through underwater cutpellet.
The key technical indexes: molecular weight distribution width (DMW): <2; Number-average molecular weight (Mn): 49000; Standard 25 DEG C of water coolant hardened forming time: <34S; Tensile strength: 45MPa; Elongation: 690%; Tear strength: 88KN/m
Embodiment 5
The antioxidant 1010 accounting for polyol quality 6 ‰ is added in reactor, account for the stannous octoate of polyol quality 200ppm, by hexanodioic acid and 1, the equal molecular mass of number of 4-butyleneglycol condensation is the polyester polyol of 2500, be put in test tank after dehydration melting mixing 5h under 95 DEG C of temperature condition and-0.08 ~-0.1MPa vacuum tightness, open test tank stir and stop vacuum and inflated with nitrogen after being evacuated to-0.085MPa, form component A for subsequent use;
By diphenylmethanediisocyanate 43.5 DEG C of meltings and vacuum is drawn in test tank, form component B for subsequent use;
By BDO 40 DEG C of meltings and vacuum is drawn in test tank ,-0.08 ~-0.1MPa vacuum tightness dehydration 4h, forms component C for subsequent use;
By the higher aliphatic alkane of C22, the high fatty alcohol of C36 and sad mono—n—butylester in mass ratio 2:1:6 high efficient mixer mix, obtain compound molecule lubricant;
By component A, component B, component C is by high class gear volume pump 50:12:38[formulating of recipe R (ratio of NCO/OH) value=0.995 in mass ratio] to be filled into mixing section ratio be 35% simultaneously, conversion zone pitch reduces in the twin screw extruder of 14% (conversion zone screw thread ratio accounts for 65% of total screw rod), setting forcing machine rotating speed is 250RPM, setting 1# ~ 6# temperature is 110 DEG C ~ 160 DEG C, 7# ~ 12# temperature is reaction mixing under the condition of 195 DEG C ~ 170 DEG C, 7# by high precision Weightlessness balance compound molecule lubricant to be added into by 8 ‰ of Polyurethane Thermoplastic Elastomer (TPU) total amount mix with TPU melt in forcing machine after obtain rapid shaping Polyurethane Thermoplastic Elastomer particle through underwater cutpellet.
The key technical indexes: molecular weight distribution width (DMW): <2; Number-average molecular weight (Mn): 38000; Standard 25 DEG C of water coolant hardened forming time: <33S; Tensile strength: 25MPa; Elongation: 510%; Tear strength: 64KN/m.
Claims (8)
1. a rapid shaping method for preparing thermoplastic polyurethane elastomer, the steps include:
1) polyester polyol is added reactor after 90 ~ 200 DEG C of meltings, then add oxidation inhibitor, catalyzer; Keep reactor temperature at 90 ~ 200 DEG C, adjustment reacting kettle inner pressure is to-0.08 ~-0.1MPa, and dehydration 0.5 ~ 8h, is then cooled to 75 ~ 115 DEG C, passes into nitrogen and removes vacuum, form component A;
Described oxidation inhibitor accounts for 2 ~ 10 ‰ of polyester polyol total mass, and described catalyzer accounts for 70 ~ 600ppm of polyester polyol total mass;
2) vulcabond is heated to 40 ~ 140 DEG C, after melting, forms component B;
3) glycol chain extender is heated to 30 ~ 120 DEG C, after complete melting, adjustment reactor pressure is to-0.08 ~-0.1MPa, and dehydration 4 ~ 6h, forms component C;
4) carbonatoms is more than or equal to the higher aliphatic alkane of 16, high fatty alcohol that carbonatoms is more than or equal to 16 in mass ratio 5:1 ~ 1:1 mix formation mixture, then add alkyl esters lubricant, mix, obtain compound molecule lubricant;
Described carbonatoms is more than or equal to the higher aliphatic alkane of 16 and the mass ratio of the mixture that formed of the carbonatoms high fatty alcohol that is more than or equal to 16 and alkyl esters lubricant is 1:1 ~ 1:5;
5) adjustment of the mixing section ratio of forcing machine is increased to 25 ~ 35%, the conversion zone threaded block pitch of forcing machine is reduced by 30 ~ 45%;
6) by component A, component B, component C in mass ratio 45:13:42 ~ 65:8:27 add in twin screw extruder simultaneously, step-reaction polymerization obtains Polyurethane Thermoplastic Elastomer, compound molecule lubricant step 4) prepared at the middle part of twin screw extruder is added in twin screw extruder and fully mixes in an extruder with Polyurethane Thermoplastic Elastomer, obtains rapid shaping Polyurethane Thermoplastic Elastomer;
The higher aliphatic alkane that described carbonatoms is more than or equal to 16 is the higher aliphatic straight-chain paraffin of C16 ~ C36; The high fatty alcohol that described carbonatoms is more than or equal to 16 is the higher aliphatic straight chain alcohol of C16 ~ C36;
Described alkyl esters lubricant is the monoesters that the aliphatic saturated monocarboxylic acid of C8 ~ C16 and the straight chain alcohol of C4 ~ C8 are formed.
2. a kind of rapid shaping method for preparing thermoplastic polyurethane elastomer according to claim 1, is characterized in that: described polyester polyol is obtained through polycondensation by di-carboxylic acid and dibasic alcohol, and the number-average molecular weight of polyester polyol is 1000 ~ 6000.
3. a kind of rapid shaping method for preparing thermoplastic polyurethane elastomer according to claim 2, is characterized in that: described di-carboxylic acid is aliphatic dicarboxylic acid or aromatic binary carboxylic acid; Described dibasic alcohol is selected from one or more in following substances: ethylene glycol, BDO, 1,6-hexylene glycol, 2，2-dimethyl-1，3-propanediol.
4. a kind of rapid shaping method for preparing thermoplastic polyurethane elastomer according to claim 1, it is characterized in that: described vulcabond is selected from 4,4 ＇-diphenylmethanediisocyanate, naphthalene diisocyanate, PPDI, 4,4 ＇-dicyclohexyl methane diisocyanate, 3,3 ＇-dimethyl diphenyl-4, one or both and above mixture in 4 ＇-vulcabond, 3,3 ＇-dimethyl-4,4 ＇-diphenylmethanediisocyanate.
5. a kind of rapid shaping method for preparing thermoplastic polyurethane elastomer according to claim 1, is characterized in that: described glycol chain extender be C4 ~ C8 straight diol, containing the symmetry of phenyl ring or asymmetrical two terminal hydroxy group things.
6. a kind of rapid shaping method for preparing thermoplastic polyurethane elastomer according to claim 1, is characterized in that: described oxidation inhibitor is selected from one or both and above mixture in antioxidant 1010, antioxidant 1076, irgasfos 168, oxidation inhibitor 626, oxidation inhibitor 245.
7. a kind of rapid shaping method for preparing thermoplastic polyurethane elastomer according to claim 1, is characterized in that: described catalyzer is selected from one or both and above mixture in stannous octoate, dibutyl tin dilaurate, lead octoate 36, two acetic acid di-n-butyl tins.
8. a kind of rapid shaping method for preparing thermoplastic polyurethane elastomer according to claim 1, is characterized in that: the addition of described compound molecule lubricant accounts for 2 ‰ ~ 10 ‰ of component A, component B and component C three total mass.
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| CN104804173B (en) * | 2015-05-18 | 2017-10-17 | 吴江市宏宇机械有限公司 | It is a kind of resistant to elevated temperatures for polyurethane elastomer of resin mould and preparation method thereof |
| EP3371234B1 (en) * | 2015-11-04 | 2023-03-29 | Basf Se | Method for producing thermoplastic polyurethanes |
| CN105646834A (en) * | 2015-12-28 | 2016-06-08 | 北京彗鑫盛世国际贸易发展有限公司 | Paint surface protection film and application thereof in vehicle film pasting |
| CN105384905A (en) * | 2015-12-31 | 2016-03-09 | 山东一诺威聚氨酯股份有限公司 | TPU (Thermoplastic Polyurethane Elastomer) material and preparation method thereof |
| CN107383853B (en) * | 2017-06-28 | 2020-02-07 | 苏州奥斯汀新材料科技有限公司 | Preparation method of high-haze high-wear-resistance thermoplastic polyurethane elastomer |
| CN107446098A (en) * | 2017-06-30 | 2017-12-08 | 苏州奥斯汀新材料科技有限公司 | A kind of high temperature resistant puncture resistant method for preparing thermoplastic polyurethane elastomer |
| CN110903634A (en) * | 2019-11-29 | 2020-03-24 | 清远新力化机有限公司 | Low-shrinkage rapid-forming TPU (thermoplastic polyurethane) for rubber wheel injection molding and preparation method thereof |
| CN111690363B (en) * | 2020-06-30 | 2022-07-19 | 浙江华峰热塑性聚氨酯有限公司 | Preparation method and application of polyurethane adhesive |
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