CN102277627A - Method for preparing polyisophthaloyl metaphenylene diamine spinning solution - Google Patents
Method for preparing polyisophthaloyl metaphenylene diamine spinning solution Download PDFInfo
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- CN102277627A CN102277627A CN2011102271254A CN201110227125A CN102277627A CN 102277627 A CN102277627 A CN 102277627A CN 2011102271254 A CN2011102271254 A CN 2011102271254A CN 201110227125 A CN201110227125 A CN 201110227125A CN 102277627 A CN102277627 A CN 102277627A
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Abstract
The invention discloses a method for preparing polyisophthaloyl metaphenylene diamine spinning solution, which comprises the following steps: (1) dissolving a polymerization inhibitor in a polar organic solvent; (2) dissolving m-phenylenediamine in a polar organic solvent in a polymerization reactor, cooling, adding mphthaloyl chloride, and performing a polymerization reaction to form polyisophthaloyl metaphenylene diamine and hydrogen chloride; (3) when the viscosity at 30 DEG C of the spinning solution rises to 65 to 75 Pa.S, adding the polymerization inhibitor solution prepared by the step (1) into the polymerization reactor to promote the stop of the polymerization reaction; and (4) adding an alkaline earth metal compound into the polymerization reactor to neutralize the hydrogen chloride, dissolving the alkaline earth metal chloride obtained by the neutralization reaction in the polymerization solution system, and thus, obtaining the polyisophthaloyl metaphenylene diamine spinning solution. In the invention, by adding the polymerization inhibitor, the polymerization reaction for forming a polymer can be stopped at any time to obtain spinning solution with proper viscosity; and the spinning solution meets the requirements of transportation and subsequent spinning process.
Description
Technical field
The present invention relates to a kind of preparation method of poly (m-phenylene isophthalmide) spinning dope.
Background technology
Fanglun 1313, English name Poly m-phenylene isophthalamide fiber, Chinese another name: a position aramid fiber, meta-aramid, aramid fiber 1313, HT-1 fiber.English another name Nomex; Conex; Phenicon.
Poly is mainly used in makes fire prevention and exotic material, as fire screen, anti-flaming gloves, fire-entry suit, heat-resisting Work Clothes, petrochemical plant Work Clothes, turnout gear etc., be characterized in that snugness of fit is good, mechanical strength is higher under the high temperature, and density is less.Also be used to make parachute, flying suit, suit, airline carriers of passengers drapery etc.The meta-aramid Nomex also is used to make the filter medium of high temperature and corrosive gas, as the filtration of flue gas, can be used for the high-temperature dust removal filtration bag that uses in metal smelt, cement, lime and the industries such as gypsum production, coking, generating and chemical industry.Transport the conveyer belt of high temperature and corrosive substance and insulating material etc.Also be used for cellular structural material, radiation resistance material.Also can mix and knit, improve anti-flammability with other flame-resistant fibres.
Domestic polymerization commonly used is a low temperature solution polymerization at present, this method is divided into two steps, step 1) m-phenylene diamine (MPD) and m-phthaloyl chloride carry out polymerisation and generate poly under lower temperature in amide solvent, produce hydrogen chloride as accessory substance simultaneously.Step 2) with alkaline earth metal compound neutralization procedure 1) described hydrogen chloride, the alkaline earth metal chloride that neutralization reaction obtains is dissolved in the molten dense system of polymerization, and this polymer solution can be directly used in spinning.As U.S. Pat P3063966.The shortcoming of this method is, can't control effectively to the viscosity of poly (m-phenylene isophthalmide) spinning dope, thereby cause the degree of polymerization of polymerisation too high.As everyone knows, poly (m-phenylene isophthalmide) spinning dope needs certain viscosity (relative viscosity is between 2.2-2.6), and viscosity is too low, and fiber does not reach requirement, and viscosity is too high, and conveying and spinning technique are all had any problem.
Summary of the invention
Deficiency at the prior art existence, technical problem to be solved by this invention provides a kind of preparation method of poly (m-phenylene isophthalmide) spinning dope, in the method, add the polymerisation that polymerization inhibitor can stop poly fast in the polymerization procedure, obtain the spinning solution that viscosity is fit to.
The preparation method of poly (m-phenylene isophthalmide) spinning dope of the present invention is achieved by the following technical solution:
A kind of preparation method of poly (m-phenylene isophthalmide) spinning dope, be made up of following step:
(1) preparation inhibitor solution: polymerization inhibitor is dissolved in the polar organic solvent;
(2) low temperature solution polymerization reaction: in polymer reactor, be dissolved in the polar organic solvent m-phenylene diamine (MPD) and cooling, add m-phthaloyl chloride and carry out polymerization, generate poly and hydrogen chloride;
(3) stop polymerization: when spinning solution viscosity rises to 65-75Pa.S, in the inhibitor solution adding polymer reactor with step (1) preparation, impel polymerisation to stop;
(4) neutralization: alkaline earth metal compound is added in the polymer reactor, the above-mentioned hydrogen chloride that neutralizes, the alkaline earth metal chloride that neutralization reaction obtains is dissolved in the polymeric solution system, makes poly (m-phenylene isophthalmide) spinning dope.
Wherein, preferably:
In the step (1), described polymerization inhibitor is simple function group monomer or water, and described simple function group monomer is chlorobenzoyl chloride or phenyl ethylamine, when polymerization inhibitor is the simple function group monomer, the mass percent of polymerization inhibitor in inhibitor solution is 5-20%, and best in quality percentage is 10-15%; When polymerization inhibitor was water, the mass percent of polymerization inhibitor in inhibitor solution was 1-10%.Best in quality percentage is 4-6%.Adopt water as polymerization inhibitor in the present invention, price is low, and is soluble in amide solvent, preserves easily.
In the step (1), when polymerization inhibitor was the simple function group monomer, the addition of simple function group monomer was the 0.2-2% of m-phenylene diamine (MPD) mole dosage, and the optimum molar consumption is 0.5-0.7%, can stop polymerisation fast, does not influence other performances again; When polymerization inhibitor was water, the addition of water was the 0.2-2% of m-phenylene diamine (MPD) mole dosage, and the optimum molar consumption is 0.8-1%, can stop polymerisation fast, did not influence other performances again.
In the step (2), m-phthaloyl chloride and m-phenylene diamine (MPD) are etc. that mol ratio adds.
In the step (2), viscosimeter is installed in the polymer reactor.The on-line monitoring solution viscosity, polymer viscosity is along with reaction raises, polymer viscosity is increased to 65-75 Pa.S(30 ℃ rotary viscosity) time, add polymerization inhibitor.
In step (1) and the step (2), described polar organic solvent is N,N-dimethylacetamide or methyl pyrrolidone.
In the step (4), the quality percentage composition of poly is 10-20% in the poly (m-phenylene isophthalmide) spinning dope that makes.
The present invention can stop the polymerisation of polymer at any time by adding polymerization inhibitor, obtains the spinning solution that viscosity is fit to (relative viscosity is between 2.2-2.6), is fit to very much carry and follow-up spinning technique requirement.
The specific embodiment
Below in conjunction with embodiment the present invention is further described.
Embodiment 1
(1) preparation inhibitor solution: the water-soluble of 0.01 weight portion in the N,N-dimethylacetamide (being called for short DMAC) of 0.27 weight portion, is made inhibitor solution.
(2) low temperature solution polymerization reaction: the m-phenylene diamine (MPD) with 1 weight portion in still formula polymer reactor is dissolved among the DMAC of 9.5 weight portions, be cooled to below-10 ℃, under agitation carry out polymerization in the m-phthaloyl chloride adding still formula polymer reactor with 1.88 weight portions, generate poly and hydrogen chloride, in the described polymer reactor viscosimeter is installed;
3) stop polymerization: the viscosity of observing response solution at any time, when viscosity arrives 30 ℃ of 65Pa.s, the inhibitor solution of step (1) preparation is added in the polymer reactor, impel polymerisation to stop;
(4) neutralization: the calcium hydroxide of 0.68 weight portion is added in the polymer reactor, above-mentioned hydrogen chloride neutralizes, the alkaline earth metal chloride that neutralization reaction obtains is dissolved in the polymeric solution system, make poly (m-phenylene isophthalmide) spinning dope, the quality percentage composition 16.3% of poly, relative viscosity are 2.38.
Embodiment 2
(1) preparation inhibitor solution: the phenyl ethylamine of 0.07 weight portion is dissolved among the DMAC of 0.48 weight portion, makes inhibitor solution.
(2) low temperature solution polymerization reaction: the m-phenylene diamine (MPD) with 1 weight portion in still formula polymer reactor is dissolved among the DMAC of 9.5 weight portions, be cooled to below-10 ℃, under agitation carry out polymerization in the m-phthaloyl chloride adding still formula polymer reactor with 1.88 weight portions, generate poly and hydrogen chloride, in the described polymer reactor viscosimeter is installed;
3) stop polymerization: the viscosity of observing response solution at any time, when viscosity arrives 30 ℃ of 71Pa.s, the inhibitor solution of step (1) preparation is added in the polymer reactor, impel polymerisation to stop;
(4) neutralization: the calcium hydroxide of 0.68 weight portion is added in the polymer reactor, above-mentioned hydrogen chloride neutralizes, the alkaline earth metal chloride that neutralization reaction obtains is dissolved in the polymeric solution system, make poly (m-phenylene isophthalmide) spinning dope, the quality percentage composition 16.3% of poly, relative viscosity are 2.47.
Embodiment 3
(1) preparation inhibitor solution: the chlorobenzoyl chloride of 0.08 weight portion is dissolved among the DMAC of 0.56 weight portion, makes inhibitor solution.
(2) low temperature solution polymerization reaction: the m-phenylene diamine (MPD) with 1 weight portion in still formula polymer reactor is dissolved among the DMAC of 9.5 weight portions, be cooled to below-10 ℃, under agitation carry out polymerization in the m-phthaloyl chloride adding still formula polymer reactor with 1.88 weight portions, generate poly and hydrogen chloride, in the described polymer reactor viscosimeter is installed;
3) stop polymerization: the viscosity of observing response solution at any time, when viscosity arrives 30 ℃ of 75Pa.s, the inhibitor solution of step (1) preparation is added in the polymer reactor, impel polymerisation to stop;
(4) neutralization: the calcium hydroxide of 0.68 weight portion is added in the polymer reactor, above-mentioned hydrogen chloride neutralizes, the alkaline earth metal chloride that neutralization reaction obtains is dissolved in the polymeric solution system, make poly (m-phenylene isophthalmide) spinning dope, the quality percentage composition 16.3% of poly, relative viscosity are 2.51.
Claims (10)
1. the preparation method of a poly (m-phenylene isophthalmide) spinning dope is characterized in that, is made up of following step:
(1) preparation inhibitor solution: polymerization inhibitor is dissolved in the polar organic solvent;
(2) low temperature solution polymerization reaction: in polymer reactor, be dissolved in the polar organic solvent m-phenylene diamine (MPD) and cooling, add m-phthaloyl chloride and carry out polymerization, generate poly and hydrogen chloride;
(3) stop polymerization: when spinning solution viscosity rises to 30 ℃ during 65-75Pa.S, the inhibitor solution of step (1) preparation is added in the polymer reactor, impel polymerisation to stop;
(4) neutralization: alkaline earth metal compound is added in the polymer reactor, the above-mentioned hydrogen chloride that neutralizes, the alkaline earth metal chloride that neutralization reaction obtains is dissolved in the polymeric solution system, makes poly (m-phenylene isophthalmide) spinning dope.
2. the preparation method of poly (m-phenylene isophthalmide) spinning dope as claimed in claim 1, it is characterized in that: in the step (1), described polymerization inhibitor is simple function group monomer or water, and described simple function group monomer is chlorobenzoyl chloride or phenyl ethylamine.
3. the preparation method of poly (m-phenylene isophthalmide) spinning dope as claimed in claim 2, it is characterized in that: when polymerization inhibitor was the simple function group monomer, the mass percent of polymerization inhibitor in inhibitor solution was 5-20%.
4. the preparation method of poly (m-phenylene isophthalmide) spinning dope as claimed in claim 2, it is characterized in that: when polymerization inhibitor was water, the mass percent of polymerization inhibitor in inhibitor solution was 1-10%.
5. the preparation method of poly (m-phenylene isophthalmide) spinning dope as claimed in claim 2, it is characterized in that: when polymerization inhibitor was the simple function group monomer, the addition of simple function group monomer was the 0.2-2% of m-phenylene diamine (MPD) mole dosage.
6. the preparation method of poly (m-phenylene isophthalmide) spinning dope as claimed in claim 2, it is characterized in that: when polymerization inhibitor was water, the addition of water was the 0.2-2% of m-phenylene diamine (MPD) mole dosage.
7. the preparation method of poly (m-phenylene isophthalmide) spinning dope as claimed in claim 1 is characterized in that: in the step (2), m-phthaloyl chloride and m-phenylene diamine (MPD) are etc. that mol ratio adds.
8. the preparation method of poly (m-phenylene isophthalmide) spinning dope as claimed in claim 1 is characterized in that: in the step (2), viscosimeter is installed in the polymer reactor.
9. the preparation method of poly (m-phenylene isophthalmide) spinning dope as claimed in claim 1, it is characterized in that: in step (1) and the step (2), described polar organic solvent is N,N-dimethylacetamide or methyl pyrrolidone.
10. the preparation method of poly (m-phenylene isophthalmide) spinning dope as claimed in claim 1, it is characterized in that: in the step (4), the quality percentage composition of poly is 10-20% in the poly (m-phenylene isophthalmide) spinning dope that makes.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110983475A (en) * | 2019-12-19 | 2020-04-10 | 超美斯新材料股份有限公司 | Preparation method of polyisophthaloyl metaphenylene diamine solution capable of controlling viscosity |
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| US5523034A (en) * | 1993-04-12 | 1996-06-04 | E. I. Du Pont De Nemours And Company | Solution of PPD-T and PVP and articles made therefrom |
| CN1974892A (en) * | 2006-11-17 | 2007-06-06 | 钟洲 | Prepn process of poly (m-phenylene isophthalmide) spinning dope |
| JP2007254525A (en) * | 2006-03-22 | 2007-10-04 | Teijin Techno Products Ltd | Method for producing meta type wholly aromatic polyamide solution |
| CN101285214A (en) * | 2008-03-18 | 2008-10-15 | 东华大学 | Preparation of low salt-containing aramid fiber 1313spinning solution and process for spinning fibre by wet method |
| JP2009287126A (en) * | 2008-05-27 | 2009-12-10 | Toray Opelontex Co Ltd | Modifier for producing elastic fiber |
| CN101876092A (en) * | 2010-07-16 | 2010-11-03 | 四川辉腾科技有限公司 | Method for producing polymetaphenylene isophthamide spinning solution |
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- 2011-08-09 CN CN2011102271254A patent/CN102277627A/en active Pending
Patent Citations (6)
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| US5523034A (en) * | 1993-04-12 | 1996-06-04 | E. I. Du Pont De Nemours And Company | Solution of PPD-T and PVP and articles made therefrom |
| JP2007254525A (en) * | 2006-03-22 | 2007-10-04 | Teijin Techno Products Ltd | Method for producing meta type wholly aromatic polyamide solution |
| CN1974892A (en) * | 2006-11-17 | 2007-06-06 | 钟洲 | Prepn process of poly (m-phenylene isophthalmide) spinning dope |
| CN101285214A (en) * | 2008-03-18 | 2008-10-15 | 东华大学 | Preparation of low salt-containing aramid fiber 1313spinning solution and process for spinning fibre by wet method |
| JP2009287126A (en) * | 2008-05-27 | 2009-12-10 | Toray Opelontex Co Ltd | Modifier for producing elastic fiber |
| CN101876092A (en) * | 2010-07-16 | 2010-11-03 | 四川辉腾科技有限公司 | Method for producing polymetaphenylene isophthamide spinning solution |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110983475A (en) * | 2019-12-19 | 2020-04-10 | 超美斯新材料股份有限公司 | Preparation method of polyisophthaloyl metaphenylene diamine solution capable of controlling viscosity |
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Address after: Friendship Industrial Zone Wujiang City Lingzhen Suzhou City, Jiangsu province 215222 Applicant after: SRO ARAMID FIBER (JIANGSU) CO., LTD. Address before: Friendship Industrial Zone Wujiang City Lingzhen Suzhou City, Jiangsu province 215222 Applicant before: Shengou(Suzhou) Safety Protection Material Co., Ltd. |
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Application publication date: 20111214 |