CN1316446A - Process for preparing iminoester additive for melt-spinning of polyurethane fibres - Google Patents
Process for preparing iminoester additive for melt-spinning of polyurethane fibres Download PDFInfo
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- CN1316446A CN1316446A CN 01112802 CN01112802A CN1316446A CN 1316446 A CN1316446 A CN 1316446A CN 01112802 CN01112802 CN 01112802 CN 01112802 A CN01112802 A CN 01112802A CN 1316446 A CN1316446 A CN 1316446A
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- polyurethane
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Abstract
A process for preparing an iminoester additive for melt-spinning of polyurethane fibres includes reaction of poly (tetramethylene butandiol) etherdiol or poly (butanediol adipate) esterdiol with diisocyanate to obtain prepolymer, latter them reacts with the compound of phenol, alcohol, ester, or amine, which contains reactive hydrogen, to temporarily protect the NCO groups at both terminals of said prepolymer, resulting in an ordinary-temp stable iminoester.
Description
The present invention is the manufacture method of the polyurethane additive used of a kind of melt spun spandex, be about to poly-(tetramethylene butyleneglycol) ether glycol or poly-(hexanodioic acid butyleneglycol) esterdiol and di-isocyanate reaction and generate performed polymer, react with the NCO group in compounds such as the phenol that has reactive hydrogen, alcohol, ester, amine and derivative and the performed polymer, generate a kind of stable at normal temperatures polyurethane additive.
The spandex melt-spinning has advantages such as technical process is simple, facility investment is few, production efficiency is high, production process is not used solvent, low in the pollution of the environment and becomes the most economic and the most friendly to environment spandex production new technology.Because melt spun spandex and the structural difference of dry spinning spandex make the thermotolerance of melt spun spandex and rebound resilience relatively poor.In order to overcome above-mentioned shortcoming, generally adopt the method for adding performed polymer both at home and abroad, yet the NCO group of performed polymer is very active, in depositing process, be easy to airborne moisture and take place to pay reaction, performed polymer was lost efficacy.So people expect a kind of polyurethane that at normal temperatures can be stable, for use in the spandex melt-spinning technology.
That the object of the invention provides is that a kind of melt spun spandex is used, stable polyurethane additive at normal temperatures.
The invention provides a kind of melt spun spandex is used, stable polyurethane additive at normal temperatures; be as end-capping reagent with compounds such as the phenol that has reactive hydrogen, acid, alcohol, ester, amine; react with the NCO group in the performed polymer; make two ends NCO group obtain temporary transient protection; reaction forms a kind of stable at normal temperatures polyurethane; formula (1) is seen in its reaction, can avoid effectively like this reacting with airborne moisture.
Formula (1) is reversible reaction, helps reaction during elevated temperature and carries out left, and the polyurethane decomposition can discharge again has active NCO group, and the reactive hydrogen generation crosslinking reaction in NCO group and the urethane generates allophanate so, and formula (2) is seen in its reaction
Formula (2) also is a reversible reaction relevant with temperature, the allophanate cross-link bond that reaction generates, be unsettled on thermodynamics, the rising of Yin Wendu in the spinning process, reaction is carried out left, allophanate is separated crosslinked, make urethane still have good processing flowability, regenerate crosslinking structure after the cooling, thereby the thermotolerance and the rebound resilience of fiber have been improved, because polyurethane is highly stable at normal temperatures, and staging life can prolong widely, therefore the dead front type performed polymer of this novelty is more effective than conventional prepolymer method simultaneously.
The present invention provides a kind of manufacture method that is used for the dead front type performed polymer of melt spun spandex.
The manufacture method of the polyurethane additive that a kind of melt spun spandex of the present invention is used, be to gather (tetramethylene butyleneglycol) ether glycol or poly-(hexanodioic acid butyleneglycol) esterdiol and di-isocyanate reaction 1~5h to generate performed polymer at 80~120 ℃, again with the phenol of the compound that contains reactive hydrogen, alcohol, ester, the compound of amine and derivative thereof and above-mentioned performed polymer are at 20~110 ℃ of reaction 1~5h, described poly-(tetramethylene butyleneglycol) ether glycol or poly-(hexanodioic acid butyleneglycol) esterdiol, vulcabond and the above-mentioned mol ratio that contains the compound of reactive hydrogen are respectively 1: 1~1,5: 2~3, described phenol, alcohol, ester, the molecular formula of amine and their derivative thereof is respectively R
1 R2OH; R3COO R4, R5R6NH2, wherein R1=H, CH3, NO2, Cl, SO3H; the alkyl or phenyl of R2=C1~C12; the alkyl of R3=C2-14, acyl group, thiazolinyl or alkylidene acid esters, R4=CH3 or C2H5, R5=C1~C14 alkyl, acyl group; R6=H, perhaps R5 and R6=cycloalkyl or ε-acyl in oneself.
The molecular weight of described polyether glycol or polyester glycol is 500~3000.But with the molecular weight 1000~2000 of polyether glycol or polyester glycol for well.
Described vulcabond can be 4,4 '-diphenylmethanediisocyanate (MDI), tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), 1,5-naphthalene diisocyanate (NDI), 4,6-Xylene Diisocyanate (XDI), ethylbenzene vulcabond (EDI), that more suitable is MDI, TDI, NDI.
Ester described in the present invention and derivative thereof can be methyl acrylate, methyl methacrylate, diethyl malonate, methyl aceto acetate or vinyl acetic monomer.In described phenol and the derivative thereof can be adjacent, or the compound of contraposition.
Amine that adopts among the present invention and derivative thereof are more suitable with amide amine or the ε-Ji Neixianan of the primary amine of C4~C10, C1~C2.
Not only technology is easy is easy to industrialization for method of the present invention, and the Td that is shown in than the PU that does not add the polyurethane additive in the practical application of polyurethane additive in the melt spun spandex spinning process improves about 35 ℃.
The present invention will be helped to understand by following embodiment, but content of the present invention can not be limited:
Embodiment 1
Take by weighing 872 gram polyethers (or polyester) glycol in 2 liter reactors, 80~110 ℃ of vacuum hydro-extractions 0.5~1 hour.Polyethers after the dehydration (or polyester) glycol is cooled to about 50 ℃.Add 240 gram MDI in reactor, logical nitrogen reacted 45 minutes down in 75~85 ℃, generated the performed polymer that two ends have the NCO group.
Embodiment 2
Generate performed polymer according to embodiment 1 experimental technique.In reactor, add 133 gram p-NPs, in 80~100 ℃ down and prepolymer reaction 2~4 hours, promptly generate the dead front type performed polymer.
Embodiment 3
Generate performed polymer according to embodiment 1 experimental technique.In reactor, add 42 gram glycol, in 80 ℃ of generation polyurethane additives with prepolymer reaction 1~2 hour down.Or in reactor, add 145 gram nonanol-s, in 100 ℃ down and prepolymer reaction 1~2 hour, promptly generate the polyurethane additive.
Embodiment 4
Generate performed polymer according to embodiment 1 experimental technique.In reactor, add 168 gram propanedioic acid second diester, in 100~110 ℃ with prepolymer reaction 3~4 hours, promptly generate the polyurethane additive.
Embodiment 5
Generate performed polymer according to embodiment 1 experimental technique.In reactor, add 67 gram n-Butyl Amine 99s, in about 30 ℃,, promptly generate the polyurethane additive with prepolymer reaction 2 hours.
Or in reactor, add 54 gram ethanamides, in about 90 ℃,, promptly generate the polyurethane additive in prepolymer reaction 2 hours.
In order to examine the reliability of the polyurethane additive that is used for melt spun spandex, the present invention has carried out the infrared spectra test with the polyurethane additive, by atlas analysis the residue content of its NCO group, calculate the degree of closure of polyurethane additive and the closure temperature of various polyurethane.
The degree of closure of table 1 polyurethane additive and deblocking temperature polyurethane additive types phenols alcohols ester class amine degree of closure (%) 65 ~ 98 90 ~ 98 20 ~ 90 90 ~ 98 deblocking temperatures (℃) 140 ~ 160 160 ~ 170 150 ~ 160 160 ~ 180
In order further to examine the actual effect of polyurethane additive in the melt spun spandex spinning process, polyurethane additive and urethane (PU) elastomerics are carried out blend, observe its fiber thermal characteristics.
Various polyurethane additives and PU elastomerics with 5~30% (in the PU weight), under 160~200C, carry out banburying, mixing granulation at the HAAKE torque rheometer, measure the softening temperature (TS) of mixture with DSC, and measure the decomposition temperature (Td) of mixture with the thermal weight loss method.The TS of 20 kinds of mixtures is at 190~205 ℃, and is very near with the TS of pure PU, and Td is at 200~260 ℃, improves about 35 ℃ than the Td of the PU that does not add the polyurethane additive.
Claims (6)
1. the manufacture method of the polyurethane additive used of a melt spun spandex, it is characterized in that will gather (tetramethylene butyleneglycol) ether glycol or poly-(hexanodioic acid butyleneglycol) esterdiol and di-isocyanate reaction 1~5h at 80~120 ℃ generates performed polymer, again with the phenol of the compound that contains reactive hydrogen, alcohol, ester, the compound of amine and derivative thereof and above-mentioned performed polymer are at 20~110 ℃ of reaction 1~5h, described poly-(tetramethylene butyleneglycol) ether glycol or poly-(hexanodioic acid butyleneglycol) esterdiol, vulcabond and the above-mentioned mol ratio that contains the compound of reactive hydrogen are respectively 1: 1~1,5: 2~3, described phenol, alcohol, ester, the molecular formula of amine and their derivative thereof is respectively R
1 R
2OH, R
3COOR
4, R
5R
6NH
2, R wherein
1=H, CH
3, NO
2, Cl, SO
3H, R
2=C
1~C
12Alkyl or phenyl, R
3=C
2-C
14Alkyl, acyl group, thiazolinyl or alkylidene acid esters, R
4=CH
3Or C
2H
5, R
5=C
1~C
14Alkyl, acyl group, R
6=H, perhaps R
6And R
6=cycloalkyl or ε-acyl in oneself.
2. according to a kind of polyurethane additives production process of claim 1, the molecular weight that it is characterized in that described polyether glycol or polyester glycol is 500~3000.
3. according to a kind of polyurethane additives production process of claim 2, the molecular weight that it is characterized in that described polyether glycol or polyester glycol is 1000~2000.
4. according to a kind of polyurethane additives production process of claim 1, it is characterized in that described vulcabond is 4,4 '-diphenylmethanediisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, 1, the 5-naphthalene diisocyanate, 4,6-Xylene Diisocyanate or ethylbenzene vulcabond.
5. according to the polyurethane additives production process of claim 1, it is characterized in that described ester and derivative thereof are methyl acrylate, methyl methacrylate, diethyl malonate, methyl aceto acetate or vinyl acetic monomer.
6. according to the polyurethane additives production process of claim 1, it is characterized in that in described amine and the derivative thereof it being C
4~C
10Primary amine or C
1~C
2Acid amides.
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CNB01112802XA CN1164637C (en) | 2001-04-29 | 2001-04-29 | Process for preparing iminoester additive for melt-spinning of polyurethane fibres |
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CN1316446A true CN1316446A (en) | 2001-10-10 |
CN1164637C CN1164637C (en) | 2004-09-01 |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101205286B (en) * | 2007-11-23 | 2010-06-02 | 东华大学 | Synthesis and modification method of thermoplastic polyurethanes for melt-spinning spandex |
CN106632980A (en) * | 2016-12-30 | 2017-05-10 | 山东诺威聚氨酯股份有限公司 | Stable NDI (naphthalene diisocyanate) prepolymer as well as preparation method and application thereof |
-
2001
- 2001-04-29 CN CNB01112802XA patent/CN1164637C/en not_active Expired - Fee Related
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101205286B (en) * | 2007-11-23 | 2010-06-02 | 东华大学 | Synthesis and modification method of thermoplastic polyurethanes for melt-spinning spandex |
CN106632980A (en) * | 2016-12-30 | 2017-05-10 | 山东诺威聚氨酯股份有限公司 | Stable NDI (naphthalene diisocyanate) prepolymer as well as preparation method and application thereof |
CN106632980B (en) * | 2016-12-30 | 2019-08-16 | 山东一诺威聚氨酯股份有限公司 | A kind of stable NDI performed polymer and its preparation method and application |
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CN1164637C (en) | 2004-09-01 |
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