CN1280997A - Process for preparing high-viscosity polyamide by chain enlargement reaction - Google Patents
Process for preparing high-viscosity polyamide by chain enlargement reaction Download PDFInfo
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- CN1280997A CN1280997A CN 99109659 CN99109659A CN1280997A CN 1280997 A CN1280997 A CN 1280997A CN 99109659 CN99109659 CN 99109659 CN 99109659 A CN99109659 A CN 99109659A CN 1280997 A CN1280997 A CN 1280997A
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Abstract
A process for preparing high-viscosity polyamide by chain expansion reaction features that the chain expanding agent which is 3.4-bihydro-3 substituted benzoxazine containing 2 benzoxazine cycles and the terminal radical of polyamide molecule take part in chain expansion reaction. Its advantages include high effect, low cost and simple process.
Description
The present invention relates to a kind of method that adopts preparing high-viscosity polyamide by chain enlargement reaction.The chainextender that is adopted is a kind of benzoxazine, and the end group of it and polymeric amide molecule reacts and plays the chain extension effect, thereby obtains high-viscosity polyamide.
High-viscosity polyamide is the raw material that is used for processing of films, bottle, tubing, high-performance fiber and engineering plastics, the method for preparing high-viscosity polyamide has the polymerization time of prolongation method, process for solid state polycondensation, anionic polymerization and chain extension method etc., production technique is simple because the chain extension method has, processing ease and facility investment are few, is suitable for small-scale production.The chain extension method is the polyamide resin with chainextender and melt-processable, reacts with forcing machine and extrudes processing, obtains full-bodied polymeric amide starting material.At the eighties initial stage, the chain extension legal system is equipped with after the high molecular weight resin rise, and people have attempted adopting the broad variety chainextender to improve the viscosity of polyamide resin.Reported the chain extending reaction of phosphite ester compound as United States Patent (USP)s in 1984 4433116 to polymeric amide, find that wherein triphenyl phosphite has good chain extension effect to various polyamide resins, in single screw extrusion machine processing, can make the relative viscosity of polyamide 6 be increased to 3.98 by 1.85, but need controlled temperature this moment is 305 ℃, when temperature is low, chain extension deleterious (285 ℃ time polymeric amide relative viscosity only reach 2.57), and have small molecules phenol to discharge in the chain extending reaction, polluting the environment has harm to human body.The German Patent 2458733 of nineteen ninety-five has been reported two oxazolines (bisoxazoline) and/or dioxazine (bisoxazine) has been improved polyamide molecular weight as chainextender, but effect is undesirable and time-dependent manner is big.Japanese Patent 01236238 has been reported and has been adopted two lactan (bislactam) to prepare superpolyamide as chainextender, makes the limiting viscosity of polyamide 6 be increased to 1.55 by 1.24; 1996, it is composite as chainextender with bisoxazoline or bisoxazine and bislactam that world patent WO96/34909 reports again, makes the polyamide 6 relative viscosity be increased to 3.69 by 2.53.But except that triphenyl phosphite, above-mentioned chainextender all exists raw materials cost higher, and the shortcoming that preparation is complicated is unfavorable for the suitability for industrialized production application.
The method of the preparing high-viscosity polyamide by chain enlargement reaction that the present invention proposes its objective is a kind of method that adopts new chainextender to prepare high-viscosity polyamide side is provided that the cost of this method is lower, the chain extension effect is obvious, has good industrial applications prospect.
The method of preparing high-viscosity polyamide by chain enlargement reaction of the present invention, chainextender adopt and contain 3 of 2 benzoxazine rings, and 4-dihydro-3 replaces benzoxazine.The chemical structural formula of chainextender is:
R is in the formula
, CH
3Or (CH
2)
3CH
3The chainextender consumption is 0.1%～1.5% of a polyamide resin weight, and consumption is preferably 1.0%～1.5% of polyamide resin weight.
The present invention is the same with the common method with preparing high-viscosity polyamide by chain enlargement reaction, polyamide resin and chainextender is extruded processing by the screw extrusion press reaction, to improve the viscosity of polyamide resin.Chainextender both can mix the back with polyamide resin and add forcing machine, also can add from the forcing machine melt zone.In the process that reaction is extruded, can also add as fillers such as stablizer, oxidation inhibitor, fire retardant, tougheners.
Chainextender consumption of the present invention is determined according to selected benzoxazine kind, polymeric amide kind, desired relative viscosity or melt viscosity.Its consumption can change in 0.1%～1.5% scope of polymeric amide weight.If the relative viscosity of polymeric amide is very low, then used in amounts is more more.The relative viscosity of high-viscosity polyamide increases along with the increase of chainextender consumption, can reach 3.5 with formic acid as the relative viscosity that solvent records.When the consumption of chainextender was too much, the gel content that can make polymeric amide was high and influence its processing and use properties.
It is the same that the present invention and the common method of reaction chain extension prepare the used equipment of high-viscosity polyamide, can adopt single screw extrusion machine also can adopt twin screw extruder, and extrusion temperature is between 200～300 ℃.
Chainextender benzoxazine of the present invention is with polyphenol or primary amine and formaldehyde or polyformaldehyde reaction preparation.Polyphenol mainly contains: dihydroxyphenyl propane, Bisphenol F, bisphenol S, '-biphenyl diphenol, Resorcinol or dihydroxy diphenyl ether; Primary amine mainly contains: aniline, methylamine, ethamine, butylamine or benzylamine, with benzoxazine intermediate and the monomer chainextender as polymeric amide, chainextender contains 2 benzoxazine rings at least.
Chainextender is the preparation method be exemplified below:
In the 250ml there-necked flask, add 100 milliliters of solvent toluenes, 0.05 mole aniline, 0.1 the water-soluble and 0.025 mole of dihydroxyphenyl propane of mole 37% formaldehyde stirs, reaction is 5 hours under reflux state, wash with water, solvent is removed in underpressure distillation, with ether washing or recrystallization, removes ether and obtains (3,4-dihydro-3-phenyl-two benzoxazines is called for short BZ1) intermediate or monomer.Replace aniline can make chainextender (3,4-dihydro-3-methyl-two benzoxazines is called for short BZ2) with quadrat method with methylamine.Replace aniline can make chainextender (3,4-dihydro-3-butyl-two benzoxazines is called for short BZ3) with quadrat method with butylamine.Embodiment 1:
Chainextender BZ1 and polyamide 6 are mixed under dry state with agitator, and the chainextender consumption is 1.0% of a polyamide 6 weight, compound is joined to react in the single screw extrusion machine by action of gravity by charging opening then and extrudes preparation high-viscosity polyamide 6.Extrusion condition is: be 220,240,260,260 ℃ from the charging opening to the head temperature, screw speed is 50rpm.Make solvent with formic acid, measure the relative viscosity of polyamide 6, the relative viscosity of polyamide 6 is increased to 3.26 by 2.3.When the chainextender consumption was 1.5%, then relative viscosity was increased to 3.5.When the chainextender consumption was 0.1%, then relative viscosity was increased to 2.35.Above gel content is 0.Embodiment 2:
Chainextender BZ1 and polyamide 6 are mixed, and the chainextender consumption is 1.0% of a polyamide 6 weight, and extrude preparation high-viscosity polyamide, extrusion condition with the twin screw extruder reaction: each section of forcing machine temperature is 200,230,240,240,230 ℃; Screw speed is 120rpm.Measure relative viscosity with formic acid, the relative viscosity of polyamide 6 is increased to 3.0 by 2.3.When the chainextender consumption was 1.5%, then relative viscosity was increased to 3.4.Gel content is 0.Embodiment 3:
Chainextender BZ1 and polyamide 66 are mixed, and the chainextender consumption is 1.0% of a polyamide 66 weight, and extrude preparation high-viscosity polyamide, extrusion condition with the twin screw extruder reaction: each section of forcing machine temperature is 200,240,260,260,240 ℃; Screw speed is 120rpm.Measure relative viscosity with formic acid, the relative viscosity of polyamide 66 is increased to 2.6 by 1.97.The chainextender consumption is 0.1%, and then relative viscosity is increased to 2.0.Gel content is 0.Embodiment 4:
Chainextender BZ3 and polyamide 6 are mixed, and the chainextender consumption is 1.0% of a polyamide 6 weight, and extrude preparation high-viscosity polyamide, extrusion condition with the single screw extrusion machine reaction: each section of forcing machine temperature is 200,240,250,250,230 ℃; Screw speed is 40rpm.Measure relative viscosity with formic acid, the relative viscosity of polyamide 6 is increased to 2.76 by 2.30.When the chainextender consumption was 0.1%, then relative viscosity was increased to 2.33.Gel content is 0.Embodiment 5:
Chainextender BZ2 and polyamide 6 are mixed, and the chainextender consumption is 1.0% of a polyamide 6 weight, and extrude preparation high-viscosity polyamide, extrusion condition with the single screw extrusion machine reaction: each section of forcing machine temperature is 200,240,250,250,230 ℃; Screw speed is 40rpm.Measure relative viscosity with formic acid, the relative viscosity of polyamide 6 is increased to 2.67 by 2.30.When the chainextender consumption was 0.1%, then relative viscosity was increased to 2.37.Gel content is 0.Embodiment 6:
Chainextender BZ2 and polyamide 66 are mixed, and the chainextender consumption is 0.1% of a polyamide 66 weight, is that 280 ℃ of reactions are extruded with single screw extrusion machine in temperature; The relative viscosity of polyamide 66 is increased to 2.0 by 1.97.Gel content is 0.Embodiment 7:
Chainextender BZ3 and polyamide 66 are mixed, and the chainextender consumption is 0.1% of a polyamide 66 weight, is that 280 ℃ of reactions are extruded with single screw extrusion machine in temperature; The relative viscosity of polyamide 66 is increased to 2.03 by 1.97.Gel content is 0.
Be suitable for polyamide resin of the present invention except that polyamide 6, polyamide 66, can also be used for the mixture of polyamide 6 10, polyamide 1010, polymeric amide 11, polymeric amide 12, copolyamide or various polymeric amide.
The used chainextender of the present invention also can be with containing 2 above benzoxazine rings except with containing 2 benzoxazine rings.Chainextender both can be directly and polymeric amide mix, together join to react in the forcing machine then and extrude by charging opening; Also polymeric amide can be added by the forcing machine charging opening, and chainextender takes the back feed way directly to join in the polyamide melt.The end group of chainextender and polymeric amide molecule reacts and plays the chain extension effect, thereby obtains high-viscosity polyamide.Chain extension of the present invention is effective, and the cost of chainextender is low, preparation technology is simple, realizes industrialization easily.
Claims (2)
1, the method for preparing high-viscosity polyamide by chain enlargement reaction, be that polyamide resin and chainextender are extruded by the screw extrusion press reaction, to improve the viscosity of polyamide resin, it is characterized in that: chainextender adopts and contains 3 of 2 benzoxazine rings, 4-dihydro-3 replaces benzoxazine, consumption is 0.1%～1.5% of a polyamide resin weight, and the chemical structural formula of chainextender is:
R is in the formula
, CH
3Or (CH
2)
3CH
3
2, require 1 described method according to profit, it is characterized in that: the consumption of chainextender is 1.0%～1.5% of a polyamide resin weight.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99109659 CN1114646C (en) | 1999-07-05 | 1999-07-05 | Process for preparing high-viscosity polyamide by chain enlargement reaction |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99109659 CN1114646C (en) | 1999-07-05 | 1999-07-05 | Process for preparing high-viscosity polyamide by chain enlargement reaction |
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| CN1280997A true CN1280997A (en) | 2001-01-24 |
| CN1114646C CN1114646C (en) | 2003-07-16 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102653590A (en) * | 2011-03-02 | 2012-09-05 | 骏马化纤股份有限公司 | Polyamide chain extension enhancer and preparation method thereof |
| CN102858852A (en) * | 2010-04-06 | 2013-01-02 | 罗地亚经营管理公司 | High-viscosity polyamide composition |
| CN108752918A (en) * | 2018-06-29 | 2018-11-06 | 三叠打印线材有限公司 | Based on the 3D printing of FDM low temperature nylon material and preparation method thereof |
| JP2019182897A (en) * | 2018-04-02 | 2019-10-24 | 株式会社豊田中央研究所 | Thermoplastic resin composition, thermoplastic resin molded body and manufacturing method therefor |
-
1999
- 1999-07-05 CN CN 99109659 patent/CN1114646C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102858852A (en) * | 2010-04-06 | 2013-01-02 | 罗地亚经营管理公司 | High-viscosity polyamide composition |
| CN102858852B (en) * | 2010-04-06 | 2016-11-02 | 罗地亚经营管理公司 | High-viscosity polyamide composition |
| CN106433110A (en) * | 2010-04-06 | 2017-02-22 | 罗地亚经营管理公司 | High-viscosity polyamide composition |
| CN106433110B (en) * | 2010-04-06 | 2019-09-06 | 罗地亚经营管理公司 | High-viscosity polyamide composition |
| CN102653590A (en) * | 2011-03-02 | 2012-09-05 | 骏马化纤股份有限公司 | Polyamide chain extension enhancer and preparation method thereof |
| JP2019182897A (en) * | 2018-04-02 | 2019-10-24 | 株式会社豊田中央研究所 | Thermoplastic resin composition, thermoplastic resin molded body and manufacturing method therefor |
| JP7102870B2 (en) | 2018-04-02 | 2022-07-20 | 株式会社豊田中央研究所 | Thermoplastic resin composition, thermoplastic resin molded product and method for producing the same |
| CN108752918A (en) * | 2018-06-29 | 2018-11-06 | 三叠打印线材有限公司 | Based on the 3D printing of FDM low temperature nylon material and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1114646C (en) | 2003-07-16 |
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