CN1179438A - Process for recovery of bisphenol-A from thermoplastic polymer containing dihydric phenol units - Google Patents
Process for recovery of bisphenol-A from thermoplastic polymer containing dihydric phenol units Download PDFInfo
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- CN1179438A CN1179438A CN 97114038 CN97114038A CN1179438A CN 1179438 A CN1179438 A CN 1179438A CN 97114038 CN97114038 CN 97114038 CN 97114038 A CN97114038 A CN 97114038A CN 1179438 A CN1179438 A CN 1179438A
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- dihydric phenol
- liquid phase
- thermoplastic polymer
- urea
- dihydroxyphenyl propane
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Abstract
A method of recovering a dihydric phenol from a composition containing a thermoplastic polymer having the reaction residue of dihydric phenol units in the polymer structure, comprises: (a) granulating a composition containing a thermoplastic polymer; (b) treating the granulated particles with an organic swelling solvent that is miscible with water and is easily distilled off from an aqueous solution to swell the particles; (c) contacting the swelled granulated particles with an aqueous ammoniacal solution to severe selectively the ester bonds of the reaction residue of the dihydric phenol units in the thermoplastic polymer and at least 25 deg C; (d) separating the liquid phase from the solid phase; (e) distilling the ammonia and the organic swelling solvent from the liquid phase; (f) adding sufficient water to the residue which contains dissolved urea and partially precipitated dihydric phenol forming a liquid and a solid phase of dihydric phenol; and (g) separating the insoluble; (h) solid dihydric phenol.
Description
The present invention relates to reclaim from a kind of composition the method for dihydric phenol, this composition contains the reaction residue that has dihydric phenol on its structure unitary thermoplastic polymer, particularly polyethers, comprises the blend of polyethers and other material.More particularly, the present invention relates to be used to produce product so that its is circulated by the dihydroxyphenyl propane that effective and the industrial recovery method of available reclaim in the polyester.
Along with the particularly appearance of thermoplastic material of work material, the problem of handling discarded thermoplastic product and material is serious day by day.Many plastics are actually non-biodegradable.Taked some steps to recycle plastics, and thisly just constantly adopted.Unfortunately recycle the thermal treatment that relates to thermoplastic material, generally like this can cause quality at thermoplastic material aspect its chemistry and the physical properties two to descend to also comparing with fresh material according to this influencing its performance.After plastics were by thermal treatment, its various performances all may degenerate, such as the deformability under shock resistance, load and the temperature, tensile strength, bending strength, extensibility, flow characteristics etc.Along with use increasing thermoplastic resin in making consuming product, a broken plastics difficult problem becomes more and more outstanding.Obviously, reclaim broken plastic waste and will be a wealth to the public and plastics industry with the method that they become useful chemical substance.
United States Patent (USP) 4885407 has been described from method broken or depleted aromatic polyester such as polycarbonate recovery dihydric phenol.This method relates to and the solution of the aqueous solution of polycarbonate and a kind of ammonia and a kind of polycarbonate such as methylene dichloride are contacted and forms two liquid phases, and the upper strata is the methylene dichloride phase for water lower floor.Be separated and methylene dichloride is evaporated from described liquid phase two.Obviously, methylene dichloride has brought environmental problem.
The present inventor finds and has developed a kind of method uncannily, and it can separate and optionally disconnect aromatic polyester effectively such as polycarbonate, the ester bond of copolyestercarbonates, poly-aryl esters etc.In brief, the inventive method comprises described aromatic polycarbonate is for example contacted for some time with an organic swelling agent such as methyl alcohol, adds the aqueous solution of ammonia then.Described ammonia solution has the ammonium salt (cabisan salt) that sufficient intensity comes selectivity to disconnect the ester bond of described polycarbonate and forms the dihydroxyphenyl propane that is soluble in the aqueous phase.Form two-phase system, i.e. a solid phase and a liquid phase, liquid phase comprises the ammonium salt of urea and dihydroxyphenyl propane.Reaching two by filtration is separated.Described solid phase comprises other material such as filler, pigment, toughener, other polymkeric substance such as acrylonitrile-butadiene-styrene (ABS) (ABS), polybutylene terephthalate (PBT) etc.By distillation boil methyl alcohol and excess ammonia of low in the described liquid phase removed.Stay water-soluble urea and the isolating dihydroxyphenyl propane of part owing to precipitate.Add enough water and from solution, be precipitated out, and pass through filtering separation up to all dihydroxyphenyl propanes.Then with solid-state dihydroxyphenyl propane drying, and its purifying and the intermediate that do fully in the chemical reaction can be used.
The present invention relates to reclaim the particularly novel method of dihydroxyphenyl propane of dihydric phenol from a kind of composition, described composition contains the unitary thermoplastic polymer of reaction residue of tool dihydric phenol in its polymer architecture.This thermoplastics preferably includes the polyester of the reaction residue that contains dihydric phenol in polymer architecture or the blend of this kind polyester and other material.The inventive method comprises:
(a) composition that will be included in the unitary thermoplastic polymer of reaction residue that has dihydric phenol in the polymer architecture is granulated;
(b) handle the granulation particle with water soluble and the easy organic swelling solvent that distills from the aqueous solution, the treatment time should be enough to make the particle swelling;
(c) under at least about 25 ℃ temperature, the ester bond that disconnects dihydric phenol units in selecting property of the thermoplastic polymkeric substance with selectivity be will contact, thereby a solid phase and a liquid phase formed through the ammonia soln of swollen particle and sufficient intensity;
(d) liquid phase is separated with solid phase;
(e) from the liquid phase of (d), distill ammonia and organic swelling solvent;
(f) in the residue of (e) that comprise the dihydric phenol that dissolves urea and partly precipitated, add enough water and make the dihydric phenol precipitation, thereby form liquid phase and dihydric phenol solid phase;
(g) solid phase and liquid phase separation are opened; With
(h) the dihydric phenol precipitation of (g) is dry.
The swelling of polymer beads is not dissolved described particle basically but has been increased the particulate free volume in the present invention.For example, alcohol does not dissolve dihydric phenol such as polycarbonate.Above disclosed recovery dihydric phenol can by such as the distillation, recrystallization, vacuum distilling, charcoal absorption or other purification process etc. are further purified in solvent.
In practice of the present invention, above the aqueous liquid phase of step (f) comprise the dissolving urea, can reclaim this urea from its aqueous solution then.But the urea that is reclaimed is purifying or to be separated into its component be ammonia and CO also
2Both or urea originally have practical use in chemical industry.
Particle size after the thermoplastics article are granulated is not crucial concerning ammonia of the present invention is separated chemistry.But for provide bigger to swelling of the present invention mutually in the exposed surface area of organic swelling solvent, the particle diameter of granulated materials is preferably about 0.2-10mm.In general, granulation is thin more, and the reaction times of the dihydric phenol of swelling time and the required output of acquisition subsequently is short more.The particulate preferred size also may be a function of described composition when the thermoplastic material granulation.Even account in the leading composition at polycarbonate, particle diameter also has favorable influence to swelling time and reaction times.Obviously, particle diameter is more little, and swelling phenomenon and reaction times are more effective.But; if being polycarbonate and other material, described composition do not contain the blend of unitary other polymkeric substance of reaction residue of dihydric phenol such as other; thinner granulation also influences swelling time and reaction times except that high surface area influences the efficient of reaction by providing more.
Time that particle described in the swelling step of the inventive method is handled with organic swelling solvent can because of particle diameter and thermoplastic materials form different.Swelling time should be enough to the described particle of swelling, and preferably its scope can be from about 10 minutes or still less to about 60 minutes or more.Described organic swelling solvent can be any organic swelling solvent water-soluble and that can distill from the aqueous solution that mixes.Best, described organic swelling solvent can be alcohol, ketone or its mixture (if they are mixable).Described alcohol can be any swellable thermoplastics particulate alcohol, preferred C
1-10Alcohol, more preferably methyl alcohol.Other included alcohol of this paper is ethanol, propyl alcohol, Virahol, butanols etc., comprises other organic alcohol.In addition, other preferred organic swelling solvent comprises any ketone, but preferred acetone, methylethylketone, isopropyl acetone etc.
After the swelling step,, added the ammonia soln of capacity in order preferably in short time cycle, optionally to disconnect the i.e. polycarbonate key for example of ester bond that thermoplastic selects dihydric phenol units in the material.Ammonia soln is that the intensity of ammonium hydroxide generally is that volumetric molar concentration is the dense ammonium hydroxide of about 18M, but the also available low all 7M according to appointment of volumetric molar concentration or lower.But the concentration of ammonia solution is low more, and it is long more required duration of contact to obtain required output dihydric phenol.Best, the mol ratio that is fit to of ammonium hydroxide and thermoplastic polymer is 4.0 to 25, particularly about 5-25.It should be understood that the ammonium hydroxide that also can use higher or lower volumetric molar concentration.In this treatment step, two-phase i.e. a solid phase and a liquid phase have been formed.
Then described solid phase and liquid phase are separated.Described liquid phase comprises the ammonium salt (dihydric phenol ammonium salt) of urea, water, methyl alcohol and dihydroxyphenyl propane.Then described liquid phase is distilled to remove methyl alcohol and excess ammonia.After distilling ammonia, the ammonium salt of dihydroxyphenyl propane (BPA) has become BPA.Stayed the aqueous solution of the dihydroxyphenyl propane of urea and partly precipitated.The water that adds capacity then in the described aqueous solution makes the precipitation of dihydroxyphenyl propane reach best.Being accomplished by filtration biphase separates.With the dry dry powder that forms of solid-state dihydroxyphenyl propane.Can be with the dihydroxyphenyl propane purifying that reclaims and be used as and particularly prepare aromatic polycarbonate, Resins, epoxy, gather a kind of reagent in the chemical reaction of other products that aryl esters and this class are reagent with the dihydroxyphenyl propane.
Fig. 1 is the schema that shows the inventive method of the program of obtaining solid-state BPA herein.The BPA that reclaims is rough BPA, but but purifying.
The polymeric material that can use in this recovery method is to be produced as one of reactant Those polymeric materials of dihydric phenol, be used for forming polymer, it comprises (but being not limited to) Aromatic polycarbonate, aromatic copolyesters carbonic ester, poly-aryl esters or its mixture or with other material Its mixture of material and/or polymer. This other material can comprise polymer such as nylon, poly-right Benzene dicarboxylic acid butanediol ester, PETG, polyphenylene ether, acrylonitrile-Butadiene-styrene (ABS) etc. Other material comprises filler (glass, carbon, mineral Matter etc.), pigment, rubber (natural or synthetic), impact modifying agent, reinforcing agent, non-Other material of filler etc. In the method these materials can with contain the poly-of dihydric phenol residue unit Compound separates.
Should point out to believe dihydroxy in described liquid phase because described solution shows ionic conductance The form of phenol is the ionic complex of ammonium hydroxide and bisphenol-A. This is by the letter as the reaction time The increase of institute's measured ion electrical conductivity of number is supported. The form of the ammonium salt of bisphenol-A is also further Confirmed by infrared analysis.
Also should understand term (containing dihydric phenol residue unit) " broken polyester " and be not limited to what is called Broken material. It can comprise that " chip " material in addition is such as not having by discarding that mold pressing changes New resin and can produce through processing of the present invention and its depolymerization the material of the bisphenol-A that will reclaim Material.
In practice of the present invention, other component of described material such as other polymer also can be and follow Ring uses and reclaims. For example, when carrying out this processing for the circulation purpose, Merlon and PBT's Blend causes the recovery of PBT. This also can be applicable to contain on other blend of dihydric phenol units, Its ester unit can optionally disconnect by this method, the other parts of callable blend.
Following embodiment will be used for illustrating situation of the present invention but and do not mean that the restriction or constriction invention disclosed herein notion.
Embodiment 1
One section of striving POLYCARBONATE SHEET (containing 99% (weight) polycarbonate basically) is granulated in a laboratory shredder.The median size of granulated materials is about 3mm.
In a lab beaker, put into about 10.5g granulation polycarbonate, add 45ml methyl alcohol (100%).With this mixture stir about 60 minutes at room temperature.Observe described polycarbonate pellets effective swelling in methyl alcohol.Add about 45ml 25% (weight) ammonium hydroxide aqueous solution (weight ratio of ammonium hydroxide and methyl alcohol is 50: 50) in swollen particle-carbinol mixture, stir about is 1 hour under about 40 ℃ temperature.Formed the two-phase of forming by a solid phase and a liquid phase.Be separated two by filtering, solid phase is dry and weigh.Mensuration shows that described solid phase accounts for about 1% (0.1g) of total polycarbonate example weight.
Then liquid phase is distilled to remove deammoniation and methyl alcohol, the ammonium salt of dihydroxy phenolic ester is transformed into the dihydric phenol form of dihydroxyphenyl propane during this period.Because in case distillation, the ammonium salt of dihydroxyphenyl propane is transformed into dihydroxyphenyl propane, so residue is a kind of solid that contains urea and dihydroxyphenyl propane.Add in the basic aqueous solution of the dihydroxyphenyl propane of dissolving urea and partly precipitated then capacity water so that dihydroxyphenyl propane with contain the urea liquid phase and separate fully.Because urea is water-soluble, therefore form two-phase, promptly because the solid phase of the water insoluble dihydroxyphenyl propane formation that produces and the liquid phase that constitutes by the aqueous solution of urea.Described bis-phenol by filter, dry, weigh and reclaim by the charcoal absorption purifying.
The outward appearance look of dihydroxyphenyl propane is a white.Mensuration shows that the dihydroxyphenyl propane (9.3g) of recovery accounts for about 99% (weight) of dihydroxyphenyl propane amount in the former polycarbonate sample.Measure and show that also the yield of urea is about 96% (weight).
Embodiment 2
Except make the blend of using about 69% (weight) polycarbonate of about 11.2g and 31% (weight) polybutylene terephthalate and other additive replace the used sample of embodiment 1 and except the reaction times be that the sample handled of methyl alcohol and the mixing time of ammonium hydroxide aqueous solution and methanol solution are about 6 hours, other is identical with embodiment 1.33% (weight) that is about original sample from the solid phase (3.62g) of this reaction recovery.
The outward appearance look of the dihydroxyphenyl propane behind the purifying that is reclaimed is a white.The dihydroxyphenyl propane that reclaims is about 99% (weight) of used dihydroxyphenyl propane in the raw sample.Reacting and separate the back with ammonium hydroxide is about 99% (weight) of polybutylene terephthalate the original sample from the polybutylene terephthalate that solids reclaims.Measure and show that also the yield of urea is about 86.5% (weight).
Embodiment 3
The sample that uses except replacement is the blend of about 59% (weight) polycarbonate and 11% (weight) ABS and other additive, repeats the process of embodiment 1 again.Its reaction times is that the sample of methyl alcohol processing and the mixing time of aqueous ammonium hydroxide and methanol solution are about 3 hours.The solid phase that reclaims from this reaction is about 42% (weight) of original sample.
The outward appearance that dihydroxyphenyl propane reclaims sample is white brown.The dihydroxyphenyl propane that reclaims is about 95% (weight) of used dihydroxyphenyl propane in the raw sample.The ABS that reclaims is about 99% of an ABS weight in the initial sample.The measurement result of urea yield is about 87% (weight).
Although the present invention has got in touch its some preferred embodiment and has been described and illustrates, those skilled in the art understand that therefore the scope of the invention is not limited to.Correspondingly, appending claims will cover all variants that drop in the spirit and scope of the present invention.
Claims (13)
1. reclaim the novel method of dihydric phenol from a kind of composition, described composition is included in the unitary thermoplastic polymer of reaction residue of tool dihydric phenol in the polymer architecture, and described method comprises:
(a) composition that will be included in the thermoplastic polymer of the reaction residue that has dihydric phenol units in the polymer architecture is granulated;
(b) handle the granulation particle with water soluble and the easy organic swelling solvent that distills from the aqueous solution, the treatment time should be enough to make the particle swelling;
(c) under at least about 25 ℃ temperature, will contact the ester bond that disconnects the reaction residue of dihydric phenol units in selecting property of the thermoplastic polymkeric substance with selectivity through the ammonia soln of swollen particle and sufficient intensity, thereby form a solid phase and a liquid phase;
(d) liquid phase is separated with solid phase;
(e) ammonia in the liquid phase and organic swelling solvent are distilled;
(f) in the residue of (e) that comprise the dihydric phenol that dissolves urea and partly precipitated, add enough water, make the dihydric phenol precipitation, thereby form liquid phase and dihydric phenol solid phase; With
(g) insoluble solid-state dihydric phenol and described liquid phase separation are opened.
2. the process of claim 1 wherein that described granulation particulate median size is about 2-25mm.
3. the process of claim 1 wherein that described organic swelling solvent is C
1-10Alcohol.
4. the method for claim 3, wherein said alcohol is methyl alcohol.
5. the process of claim 1 wherein that described organic swelling solvent is a kind of ketone.
6. the method for claim 5, wherein said ketone is acetone.
7. the process of claim 1 wherein that swollen granulation particle and contacting of ammonia soln are to carry out under about 30-50 ℃ temperature.
8. the process of claim 1 wherein that the liquid phase of step (f) is the solution of urea.
9. the method for claim 8 wherein reclaims urea by the method that vacuum distilling dewaters from described solution.
10. the process of claim 1 wherein the dihydric phenol that reclaims by the charcoal adsorption and purification.
11. the process of claim 1 wherein described composition mainly comprise be selected from polycarbonate, copolyestercarbonates, poly-aryl esters, its blend and with the polymkeric substance of the blend of other polymkeric substance.
12. the process of claim 1 wherein that the dihydric phenol that is reclaimed by this method is a dihydroxyphenyl propane.
13. the polycarbonate of the dihydroxyphenyl propane preparation that obtains by the method for claim 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97114038 CN1179438A (en) | 1996-07-01 | 1997-06-27 | Process for recovery of bisphenol-A from thermoplastic polymer containing dihydric phenol units |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US673,990 | 1996-07-01 | ||
| CN 97114038 CN1179438A (en) | 1996-07-01 | 1997-06-27 | Process for recovery of bisphenol-A from thermoplastic polymer containing dihydric phenol units |
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| Publication Number | Publication Date |
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| CN1179438A true CN1179438A (en) | 1998-04-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97114038 Pending CN1179438A (en) | 1996-07-01 | 1997-06-27 | Process for recovery of bisphenol-A from thermoplastic polymer containing dihydric phenol units |
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| CN (1) | CN1179438A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101990453A (en) * | 2008-04-02 | 2011-03-23 | 拜尔材料科学股份公司 | Particles Obtainable by Drying Aqueous Nanourea Dispersions |
| CN103664513A (en) * | 2012-09-25 | 2014-03-26 | 上海华明高技术（集团）有限公司 | Method for hydrolyzing aromatic polyester composite material and recovering monomer |
| CN105658712A (en) * | 2013-10-15 | 2016-06-08 | 沙特基础全球技术有限公司 | Method for direct ammonolysis of polycarbonate-containing materials and products |
-
1997
- 1997-06-27 CN CN 97114038 patent/CN1179438A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101990453A (en) * | 2008-04-02 | 2011-03-23 | 拜尔材料科学股份公司 | Particles Obtainable by Drying Aqueous Nanourea Dispersions |
| CN103664513A (en) * | 2012-09-25 | 2014-03-26 | 上海华明高技术（集团）有限公司 | Method for hydrolyzing aromatic polyester composite material and recovering monomer |
| CN103664513B (en) * | 2012-09-25 | 2015-12-16 | 上海华明高技术（集团）有限公司 | Aromatic polyester composite material hydrolysis and the method reclaiming monomer |
| CN105658712A (en) * | 2013-10-15 | 2016-06-08 | 沙特基础全球技术有限公司 | Method for direct ammonolysis of polycarbonate-containing materials and products |
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