CN1495220A - Method for stabilizing 4,6-diaminoresorcinol and its salt - Google Patents
Method for stabilizing 4,6-diaminoresorcinol and its salt Download PDFInfo
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- CN1495220A CN1495220A CNA031530982A CN03153098A CN1495220A CN 1495220 A CN1495220 A CN 1495220A CN A031530982 A CNA031530982 A CN A031530982A CN 03153098 A CN03153098 A CN 03153098A CN 1495220 A CN1495220 A CN 1495220A
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Abstract
The method for stabilizing DAR in storage includes storage of DAR in the presence of reductant with standard redox potential of that is not less than -0.20V and is not greater than 0.34V, and the ratio of reductant and DAR is not less than 100 ppm and is not greater than 10000 ppm. It raises the storage stability of DAR, can make the DAR be easily treated and stored for a long period, so that the high-quality polymer PBO can be easily made.
Description
The application is to be the dividing an application of the Chinese invention patent application that is entitled as " stablizing 4, the method for 6-diamino resorcin and salt thereof " on September 24th, 1998 applying date, the Chinese patent application of original application numbers 98120395.7.
Technical field
The present invention relates to have 4 of good storage stability, 6-diamino resorcin and salt thereof (hereinafter generally being referred to as DAR).The invention still further relates to the method for stablizing DAR.
Background technology
DAR is considered to prepare the raw material of polyphenyl and Er isoxazole (hereinafter being referred to as PBO) usually, and described PBO can be processed into the height strong fibre with high elastic coefficient.Can synthesize PBO by various method, these methods comprise as at uncensored Japanese Patent prospectus 242604/1995 and 136/1990, US 5,410,083 and 5,453, use Resorcinol described in 542 is as the method for raw material, as at the use trichlorobenzene described in the Japanese PCT patent application prospectus 500743/1990,502028/1993 as the method for raw material and as in the method for the use Meta Dichlorobenzene described in uncensored Japanese Patent prospectus 238561/1989 and 24038/1991 as raw material.People expect the industrialization of DAR for a long time.
On the other hand, DAR has easily oxidized shortcoming.For example, when it was in the atmosphere, because it can be oxidized in several days or it can be oxidized in several hrs when oxidizing reaction is faster, so DAR will decolour.If the polymerization of the DAR raw material by this decolouring prepares PBO, then can only obtain decolouring for green to purple and have the polymkeric substance of low polymerization degree.Therefore need in inert atmosphere, store and handle DAR and need finish-drying DAR.Even under such environment, after the standing storage of some months, the degraded that is caused by oxygenizement also is inevitable.So, the PBO moulding product (for example fiber and film) that can not obtain to have advantageous property and quality with prior art.
The Japanese patent laid-open publication gazette specification sheets of having examined 21166/1994 has proposed to add the reductibility oxide compound of phosphorus or sulphur so that obtain high-quality PBO in polymerization process.The purpose that adds the reductibility oxide compound of phosphorus or sulphur is to suppress the decomposition of DAR in the polymerization process, but does not overcome the bad storage stability of DAR.
In addition, US 5,142, and 021 has proposed to add tin chloride in polymerization process, and its purpose is identical with the Japanese patent laid-open publication gazette specification sheets of having examined 21166/1994.
Disclose among the embodiment of unexamined Japanese Patent prospectus 136/1990 in the process of preparation DAR and added tin chloride.One of purpose is used as active intermediate, i.e. nitro-1, the hydrogenation reagent of 3-dihydroxy-benzene.Another purpose is to reduce the tin chloride foreign matter content by recrystallization in purification process.Like this, do not have tin chloride in the storage of DAR, the adding of tin chloride does not overcome the bad storage stability of DAR.
Summary of the invention
As mentioned above, the synthetic method of DAR has been carried out positive research and proposed many technology.Yet, also do not find the stabilization technique of DAR and realize the suitability for industrialized production of DAR.Therefore the DAR that the purpose of this invention is to provide storage stability with improvement.
The present invention also provides the method for stablizing DAR in storage.
The invention provides by adding the DAR of the storage stability that certain reductive agent obtains with obvious improvement.
Therefore, provided by the invention theing contents are as follows:
(1) a kind of composition, basically by 4,6-diamino resorcin or its salt and having is not less than-and 0.20V and the reductive agent that is not higher than the standard redox potential of 0.34V form, and the ratio of contained reductive agent and DAR is for being not less than 100ppm and not being higher than 10,000ppm.
(2) prepare the method for polyphenyl and Er isoxazole, be included in have be not less than-0.20V and the reductive agent that is not higher than the standard redox potential of 0.34V exist down, with 4,6-diamino resorcin and aromatic dicarboxylic acid reaction, the ratio of reductive agent and DAR is for being not less than 100ppm and not being higher than 10,000ppm.
(3) in storage, stablize 4, the method of 6-diamino resorcin or its salt, be included in have be not less than-there is storage 4 down in 0.20V and the reductive agent that is not higher than the standard redox potential of 0.34V, 6-diamino resorcin or its salt, the ratio of reductive agent and DAR is for being not less than 100ppm and not being higher than 10,000ppm.
Embodiment
Hereinafter will explain the present invention in more detail.
In the present invention, can obtain DAR with ordinary method.For example, can use at Japanese PCT patent application prospectus 500743/1990, uncensored Japanese Patent prospectus 242604/1995 and 136/1990, US 5,410,083 and 5,453,542, the method described in the Japanese PCT patent application prospectus 502028/1993, uncensored Japanese Patent prospectus 238561/1989 and 24038/1991 etc.
The DAR that obtains with aforesaid method generally uses with the form of dihydrochloride.In the present invention, DAR is not limited to the form of dihydrochloride, and can be the inorganic acid salt of for example dithionate and diphosphate or the organic acid salt of terephthalate and diacetin for example.
Reductive agent among the present invention is to have to be not less than-0.20V and be not higher than 0.34V, preferably is not less than 0.0V and is not higher than the compound of the standard redox potential of 0.20V.DAR and terephthalic acid be dissolved in polymerization prepares PBO in the Tripyrophosphoric acid.In the process of preparation PBO, when DAR is dissolved in the Tripyrophosphoric acid, be lower than-reductive agent and the phosphatase reaction of 0.20V standard redox potential owing to have, will produce hydrogen unfriendly.When standard redox potential is higher than 0.34V, the DAR instability.
The example of reductive agent comprises metal-salt among the present invention, for example, and TiCl
3, CuCl, SnCl
2Deng, the reductibility oxide compound of phosphorus or sulphur, for example, Hypophosporous Acid, 50 and Sulfothiorine etc.In order to reach obvious effects with a small amount of reductive agent, wherein special preferable alloy muriate for example, TiCl
3, CuCl, SnCl
2Especially, colourless SnCl
2And hydrate is most preferred.
In the present invention, the amount of reductive agent changes with its kind.The amount of reductive agent must be constant in the 100ppm that is not less than DAR or its salt at least in the storage of DAR, preferably is not less than 1, and 000ppm more preferably is not less than 2,000ppm.When it is lower than 100ppm, can not fully stablize DAR.The stabilising effect of this degree does not produce any problem for short-term storage and use, but for standing storage, is not enough as the storage some months.When its content is 10, during 000ppm, stabilising effect is sufficient.And content is greater than 10, and the result that 000ppm only can cause higher cost and bring us not expect in PBO produces for example, makes to have a large amount of reductive agents as pollutent in the solvent slop.Preferably in the preparation process of DAR, for example, in precipitation or exsiccant process, add reductive agent.Reductive agent adds at once with the molten state adding or after being dissolved in it in volatile solvent soln.Adding affiliation with solid state hinders the uniform mixing of reductive agent and DAR and may cause partial decomposition.Gained DAR preferably is loaded with even reductive agent attached to its plane of crystal.
DAR of the present invention with said structure can be used as the raw material of PBO especially.The PBO that uses DAR and aromatic dicarboxylic acid to obtain is homopolymer or the multipolymer with following formula (I) structural unit.
Have now found that,,, also can obtain having the polymkeric substance of the quality that high-polymerization degree becomes reconciled even DAR then of the present invention and air kept in touch more than 3 months if prepare above-mentioned PBO by the polymerization of above-mentioned DAR.
Wherein, Z is the divalent aromatic organic radical with following formula (II)-(V) expression.
Wherein, in formula (II)-(V), R
1And R
2Can be identical or different and each be H, OH, have alkyl, an OR of 1-4 carbon atom
3Or halogen atom, wherein R
3It is alkyl with 1-4 carbon atom.
In many patents, proposed PBO is made the method for fiber.Use the PBO that DAR of the present invention makes can be by with known method itself, for example, be used in that disclosed method makes in US 5296185 and 5294390.Can also make film with known method own.
Hereinafter described a preferred embodiment of the present invention, the present invention is not limited.Synthesize 4 according to disclosed method in the Japanese PCT patent application prospectus 500743/1990, the dihydrochloride of 6-diamino Resorcinol.As reductive agent, the hydrochloric acid soln of tin chloride (II) or its hydrate evenly is sprayed on the DAR.Then,, mixture is carried out vacuum-drying, obtain containing 100-10, the DAR of 000ppm tin chloride (II) by in moisture eliminator, heating and stir at 40-100 ℃.Gained DAR can be used immediately subsequently.In order to evaluate its storage stability, can make DAR under 30 ℃, contact 2 months, and prepare PBO by polymerization with atmosphere.
For polymerization prepares PBO, the amount of regulating raw material is so that obtain the polymer concentration of 5-20 weight %.With the method for describing among the US 4533693 for example, 70-220 ℃ of heating and mix above obtain 4, the dihydrochloride of 6-diamino Resorcinol, ground terephthalic acid, polyphosphonic acid (105-120%) and Vanadium Pentoxide in FLAKES.The result obtains having the yellow spinning solution polymkeric substance of high-polymerization degree.
Usually be not less than under 100 ℃ the temperature, the polymkeric substance that obtains is added spinning part and deriving by spinning nozzle.With stress isolation device (stress isolator), for example, godet wheel is collected the spinning solution (being fiber yarn before the extraction of Tripyrophosphoric acid) of deriving with constant speed and is drawn in non coagulation gas.After sending into the coagulating bath that contains the aqueous solution or alcoholic solution at the fiber seal wire, by the cooling curing dope fiber.By the process of the fiber yarn behind coagulating bath godet wheel.At last, wash in the extraction tank that contains water, methyl alcohol etc. that concentration of phosphoric acid is not higher than 1.0% in fiber, preferably be not higher than 0.5%.With also further washing with water with above-mentioned bundle fiber in the aqueous solution of sodium hydroxide.After so handling, in moisture eliminator, carry out drying with high temperature air.The ultimate fibre of resulting formation bundle fiber has the sufficient intensity that is not less than 35g/d and is not less than enough Young's modulus of about 1000g/d.
Further describe the present invention with following embodiment, the present invention is not limited.In an embodiment, be dissolved in DAR in the 1N aqueous hydrochloric acid and measure UV spectrum, according to the degree of decomposition of calculating DAR in the absorption (degradation production by DAR produces) at 320nm place.Make solvent with methylsulfonic acid, 25 ℃ of limiting viscosities of measuring PBO.
Embodiment 1: the application of reductive agent
Tin chloride (II) (4g) is dissolved in and obtains the 2mol/l tin chloride solution in the 20ml aqueous hydrochloric acid.
With this solution spray equably in that the method described obtains with Japanese PCT patent application prospectus 500743/1990 4, on the 6-diamino resorcin dihydrochloride (1000g).Then, when on rotatory evaporator, stirring, under reduced pressure, be dried.Temperature remains 40 ℃-100 ℃ in the drying process.After the drying,, be scaled SnCl with the Bivalent Tin among the polarography determination DAR (equipment of use: buy 693VAProcessor, 694VA Stand, 685Dosimat from Metrom company)
2, its content is 1800ppm, 2880ppm.This DAR was preserved 3 months in air at 30 ℃, measure its degree of decomposition, be found to be 0.0%.
Embodiment 2: polymerization obtains PBO
With the DAR polymerization that obtains among the embodiment 1, obtain polyparaphenylene benzo Er isoxazole (PBO).Specifically, in nitrogen atmosphere, Vanadium Pentoxide in FLAKES (14.49kg) joined in 116% the Tripyrophosphoric acid (43.86kg).Then, add 4 among the embodiment 1,6-diamino resorcin dihydrochloride and ground median size are the terephthalic acid (7.10kg) of 2 μ m, in reactive tank mixture are stirred and mix at 80 ℃.Further be heated and mix 10 hours at 150 ℃, polymerization in being heated to 200 ℃ twin screw extruder machine obtains the polymer spun silk stock solution of cis-polyparaphenylene benzo Er isoxazole.It is yellow that this polymer spun silk stock solution is, and its limiting viscosity is 38dl/g.
Embodiment 3: the preparation of fiber
The spinning solution that obtains among the embodiment 2 is delivered to toothed gear pump by extruding machine, when keeping temperature to be 170 ℃ simultaneously.Spinning solution is twisted flax fibers and woven from spinning nozzle at 170 ℃ with 668 holes.With the fiber yarn that cooling air pumps 60 ℃ of coolings, make it to contact with phosphate aqueous solution and collect with godet wheel.
Fiber phosphorus acid content in fiber that washing obtains is 0.5 weight %, neutralizes with aqueous sodium hydroxide solution.Further wash fiber with water and 200 ℃ of dryings.The intensity of gained fiber is 38g/d, and Young's modulus is 1034g/d.
The comparative example 1
Will be under the situation of no reductive agent according to the method synthetic of describing in the Japanese PCT patent application prospectus 50,074,3/1,990 4,6-diamino resorcin dihydrochloride was preserved 3 months in air at 30 ℃.Measure its degree of decomposition, be found to be 0.38%.With the method polymerization identical with embodiment 2 this 4,6-diamino resorcin dihydrochloride, the result, it is green that the resulting polymers spinning solution is, limiting viscosity is 18dl/g.
Embodiment 4-7
Add reductive agent listed in the table 1 and replace adding tin chloride (II), in addition, use the method preparation 4 identical, 6-diamino resorcin dihydrochloride with embodiment 1.Gained DAR was preserved 3 months in air at 30 ℃.Measure its degree of decomposition, find to be 0.31 weight % in each embodiment.The polymer spun silk stock solution that obtains by polymerization DAR with the method identical with embodiment 2 is yellow, and limiting viscosity is 35-48dl/g.
The comparative example 2
Add Pd and replace adding tin chloride (II), in addition, use the method identical to prepare DAR with embodiment 1 as reductive agent.Gained DAR was preserved 3 months in air at 30 ℃.Measure its degree of decomposition, be found to be 0.31 weight %.Be purple with the method identical with embodiment 2 by the polymer spun silk stock solution that this DAR of polymerization obtains, limiting viscosity is 12dl/g.
The comparative example 3
Add the zinc powder be dispersed in the water and replace adding tin chloride (II), in addition, use the method identical to obtain DAR with embodiment 1 as reductive agent.Gained DAR was preserved 3 months in air at 30 ℃.It is indefinite to measure its degree of decomposition of its degree of decomposition, is 0.02-0.28 weight %, and DAR is the purple particulate.The polymer spun silk stock solution that this DAR of polymerization obtains is Huang-green, and limiting viscosity is 34dl/g.In polymerization process, will produce very difficulty of hydrogen and operation.
The DAR and the PBO of evaluation gained in embodiment and comparative example, gained the results are shown in the following table 1.
Table 1
| Embodiment 2 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | The comparative example 1 | The comparative example 2 | The comparative example 3 | |
| Reductive agent | ??SnCl 2 | ??TiCl 3 | ??CuCl | ??H 3PO 3 | ??H 2SO3 | ??- | ??Pd | ??Zn |
| Standard redox potential (volt) | ??0.15 | ??0.04 | ??0.153 | ??-0.20 | ??0.17 | ??0.83 | ?-0.763 | |
| Add-on (ppm) | ??2880 | ??3860 | ??5300 | ??5300 | ?420 | ??2400 | ?2800 | |
| Degree of decomposition (%) | ??0.0 | ??0.0 | ??0.0 | ??0.0 | ?0.0 | ???0.38 | ??0.31 | ?0.02- ?0.28 |
| Limiting viscosity (dl/g) | ??38 | ??48 | ??43 | ??44 | ?35 | ???18 | ??12 | ?34 |
| The spinning solution color | Yellow | Yellow | Yellow | Yellow | Yellow | Green | Purple | Yellow-green colour |
| Remarks | ? *1 | ? *2 | ? *3 |
*1,
*2:DAR is colored.
*3: in polymerization process, produce hydrogen
As seen from Table 1, the present invention has improved 4, the storage stability of 6-diamino resorcin, thus make it be easy to handle and standing storage.Therefore, can be easy to make high quality P BO polymkeric substance, the present invention helps industrial circle very much.
Because method of the present invention, DAR is no less than 1 year in storing under the room temperature to be no less than 1 month or to store under room temperature in nitrogen atmosphere in air, can not cause degraded because of oxidizing reaction.The PBO that obtains thus also has the good characteristic of high-polymerization degree.
Claims (2)
1. the method for preparing polyphenyl and Er isoxazole, be included in have be not less than-0.20V and the reductive agent that is not higher than the standard redox potential of 0.34V exist down, with 4,6-diamino resorcin or its salt and aromatic dicarboxylic acid reaction, reductive agent and 4, the ratio of 6-diamino resorcin is for being not less than 100ppm and not being higher than 10,000ppm.
2. one kind is used to prepare the also composition of two isoxazoles of polyphenyl, basically by 4,6-diamino resorcin or its salt and having is not less than-and 0.20V and the reductive agent that is not higher than the standard redox potential of 0.34V form, contained reductive agent and 4, the ratio of 6-diamino resorcin is for being not less than 100ppm and not being higher than 10,000ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03153098 CN1273518C (en) | 1998-09-24 | 1998-09-24 | Method for stabilizing 4,6-diaminoresorcinol and its salt |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03153098 CN1273518C (en) | 1998-09-24 | 1998-09-24 | Method for stabilizing 4,6-diaminoresorcinol and its salt |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB981203957A Division CN1148342C (en) | 1998-09-24 | 1998-09-24 | Processfor stabilizing 4,6-diamino resorcinol and salt thereof |
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|---|---|
| CN1495220A true CN1495220A (en) | 2004-05-12 |
| CN1273518C CN1273518C (en) | 2006-09-06 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105461575A (en) * | 2015-12-31 | 2016-04-06 | 江苏尚莱特医药化工材料有限公司 | Preparation method of 4,6-diamidoresorcinol or salts thereof |
-
1998
- 1998-09-24 CN CN 03153098 patent/CN1273518C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105461575A (en) * | 2015-12-31 | 2016-04-06 | 江苏尚莱特医药化工材料有限公司 | Preparation method of 4,6-diamidoresorcinol or salts thereof |
| CN105461575B (en) * | 2015-12-31 | 2018-07-03 | 江苏尚莱特医药化工材料有限公司 | The preparation method of 4,6- diamino resorcins or its salt |
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| CN1273518C (en) | 2006-09-06 |
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