Use of Novel catalyst and method for treating PCB inked polymer waste by the novel catalyst

Abstract

A novel catalyst, a use thereof and a method for treating PCB inked waste by using the same are disclosed. The catalyst of the present disclosure is represented by the following formula (I):

[M(O).sub.a].sup.m+X.sup.n(I)

herein M, X, a, m and n are defined in the specification.

Claims

1. A catalyst, representing by the following formula (I):
[M(O).sub.a].sup.m+X.sup.n(I) wherein M is an element of Group IB, Group IVB, Group VB, Group VIB, Group VIIB or Group VIIIB; X is Cl, Br, I, OAc, OC(O)(CF.sub.2).sub.nCF.sub.3, OC(O)C.sub.12H.sub.25, [(OSO.sub.2C.sub.6H.sub.4-CHCH.sub.2).sub.n], OTf, OTs, SO.sub.4, SO.sub.3C .sub.2H.sub.25 or acetylacetonate (acac); a is an integral of 0 to 3; m is an integral of 2 to 4; and n is an integral of 1 or 2.

2. The catalyst of claim 1, wherein a is 0, and M is Ti, Zr, Hf, V, Fe, Cu or Mn.

3. The catalyst of claim 1, wherein M(O).sub.a is VO, VO.sub.3, ZrO, HfO, WO.sub.2, MoO.sub.2, CrO.sub.2 or ReO.sub.3.

4. A use of a catalyst for degrading inks or acylating or recycling polymers, wherein the catalyst is representing by the following formula (I):
[M(O).sub.a].sup.m+X.sup.n(I) wherein M is an element of Group IB, Group IVB, Group VB, Group VIB, Group VIIB or Group VIIIB; X is Cl, Br, I, OAc, OC(O)(CF.sub.2).sub.nCF.sub.3, OC(O)C.sub.12H.sub.25, [(OSO.sub.2C.sub.6H.sub.4-CHCH.sub.2).sub.n], OTf, OTs, SO.sub.4, SO.sub.3C.sub.12H.sub.25 or acetylacetonate (acac); a is an integral of 0 to 3; m is an integral of 2 to 4; and n is an integral of 1 or 2.

5. A method for treating a PCB inked polymer waste, comprising the following steps: mixing a PCB inked polymer waste, a catalyst representing by the following formula (I), a reagent and a first solvent to obtain a mixture:
[M(O).sub.a].sup.m+X.sup.n(I) wherein M is an element of Group IB, Group IVB, Group VB, Group VIB, Group VIIB or Group VIIIB; X is Cl, Br, I, OAc, OC(O)(CF.sub.2).sub.nCF.sub.3, OC(O)C.sub.12H.sub.25, [(OSO.sub.2C.sub.6H.sub.4-CHCH.sub.2).sub.n], OTf, OTs, SO.sub.4, SO.sub.3C.sub.12H.sub.25 or acetylacetonate (acac); a is an integral of 0 to 3; m is an integral of 2 to 4; and n is an integral of 1 or 2; reacting the mixture at a predetermined temperature to obtain a reacted mixture; and adding the reacted mixture into a second solvent.

6. The method of claim 5, wherein the reagent is an anhydride-based compound, a sulfonic anhydride-based compound, an acyl halide-based compound, a sulfonyl halide-based compound, an oxidant, or a combination thereof.

7. The method of claim 6, wherein the anhydride-based compound is represented by the following formula (II):
R.sub.1C(O)OC(O)R.sub.1 (II) wherein each R.sub.1 and R.sub.1 independently is C.sub.1-C.sub.6 alkyl, CF.sub.3, C.sub.2F.sub.5, C.sub.3F.sub.7 or aryl.

8. The method of claim 6, wherein the sulfonic anhydride-based compound is represented by the following fora ula (III):
R.sub.2SO.sub.2OSO.sub.2R.sub.2 (III) wherein each R.sub.2 and R.sub.2 independently is C.sub.1-C.sub.6 alkyl, CF.sub.3, C.sub.2F.sub.5, C.sub.3F.sub.7 or aryl.

9. The method of claim 6, wherein the acyl halide-based compound is represented by the following formula (IV):
R.sub.3C(O)X(IV) wherein R.sub.3 is C.sub.1-C.sub.6 alkyl, CF.sub.3, C.sub.2F.sub.5, C.sub.3F.sub.7 or aryl; and X is Cl or Br.

10. The method of claim 6, wherein the sulfonyl halide-based compound is represented by the following formula (V):
R.sub.4SO.sub.2X(V) wherein R.sub.4 is C.sub.1-C.sub.6 alkyl, CF.sub.3, C.sub.2F.sub.5, C.sub.3F.sub.7 or aryl; and X is Cl or Br.

11. The method of claim 6, wherein the oxidant is peroxy acid-based compounds, peroxy sulfate-based compounds, NaOCl, NaO.sub.2Cl, NaO.sub.3Cl, NaO.sub.4Cl, H.sub.2O.sub.2, H.sub.2O.sub.2-urea, t-BuOOH, cumene-OOH, or Ar.sub.3COOH.

12. The method of claim 11, wherein the peroxy acid-based compound is represented by the following formula (VIA):
R.sub.5C(O)OOH (VIA) wherein R.sub.5 is C.sub.1-C.sub.6 alkyl, CF.sub.3, C.sub.2F.sub.5, C.sub.3F.sub.7 or aryl. wherein the peroxy sulfate-based compound is represented by the following formula (VIB):
MOSO.sub.2OOH (VIB) wherein M is Na or K.

13. The method of claim 5, wherein the first solvent is a carboxylic acid-based solvent, a sulfonic acid-based solvent, a phosphoric acid solvent or a combination thereof.

14. The method of claim 13, wherein the carboxylic acid-based solvent is represented by the following formula (VII):
R.sub.6CO.sub.2H (VII) wherein R.sub.6 is C.sub.1-C.sub.6 alkyl, CF.sub.3, C.sub.2F.sub.5, C.sub.3F.sub.7 or aryl..

15. The method of claim 13, wherein the sulfonic acid-based solvent is represented by the following formula (VIII):
R.sub.7SO.sub.3H (VIII) wherein R.sub.7 is C.sub.1-C.sub.6 alkyl, CF.sub.3, C.sub.2F.sub.5, C.sub.3F.sub.7 or aryl.

16. The method of claim 5, wherein the second solvent is water, alcohol, acetic acid or a combination thereof.

17. The method of claim 5, wherein the predetermined temperature is between 40 C. and 110 C.

18. The method of claim 5, wherein an amount of the catalyst is 0.5-10 wt % of a total weight of the mixture.

19. The method of claim 5, wherein in the formula (I), a is 0, and M is Ti, Zr, Hf, V, Fe, Cu or Mn.

20. The method of claim 5, wherein in the formula (I), M(O).sub.a is VO, VO.sub.3, ZrO, HfO, WO.sub.2, MoO.sub.2, CrO.sub.2 or ReO.sub.3.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0034] FIG. 1 and FIG. 2 are .sup.1H NMR spectra of porducts generated at different stages according to Example 1 of the present disclosure.

[0035] FIG. 3 is a .sup.1H NMR spectrum of a product of Example 2 of the present disclosure.

DETAILED DESCRIPTION OF EMBODIMENT

[0036] The following embodiments when read with the accompanying drawings are made to clearly exhibit the above-mentioned and other technical contents, features and effects of the present disclosure. Through the exposition by means of the specific embodiments, people would further understand the technical means and effects the present disclosure adopts to achieve the above-indicated objectives. Moreover, as the contents disclosed herein should be readily understood and can be implemented by a person skilled in the art, all equivalent changes or modifications which do not depart from the concept of the present disclosure should be encompassed by the appended claims.

[0037] Catalyst Synthesis

[0038] In the present embodiment, the catalyst can be synthesized according to the following equations.

V(O)SO.sub.4(aq)+BaX.sub.2(aq).fwdarw.V(O)X.sub.2(aq)+BaSO.sub.4(s)

V(O)SO.sub.4(aq)+Ba(OAc).sub.2(aq).fwdarw.V(O)(OAc).sub.2(aq)+BaSO.sub.4(s)

V(O)SO.sub.4(aq)+Ba(OTf).sub.2(aq).fwdarw.V(O)(OTf).sub.2(aq)+BaSO.sub.4(s)

V(O)SO.sub.4(aq)+Ba(OTs).sub.2(aq).fwdarw.V(O)(OTs).sub.2(aq)+BaSO.sub.4(s)

V(O)SO.sub.4(aq)+Ba[(O.sub.3SC.sub.6H.sub.4CHCH.sub.2).sub.n].sub.2(aq).fwdarw.V(O)[(O.sub.3SC.sub.6H.sub.4CHCH.sub.2).sub.n].sub.2(aq)+BaSO.sub.4(s)

[0039] 2.5 mmol VOSO.sub.4-5H.sub.2O was placed into a dried two-neck round-bottom flask (50 mL), followed by adding anhydrous MeOH (2.5 mL). At room temperature, a methaol solution (2.5 mL) containing 2.5 mmol (1 equiv) BaX.sub.2 (for example, Ba(OAc).sub.2, BaOTs.sub.2, BaOTf.sub.2 or Ba[(O.sub.3SC.sub.6H.sub.4CHCH.sub.2).sub.n].sub.2) was slowly added into the obtained solution. After stirring for 30 mins, the reacting mixture was turbid with a great mound of BaSO.sub.4 percipitated. The mixture was filtered through a celite plug. The obained filtrate was evaporated, and a dark blue solid was obtained. The obtained solid was dried at 120 C., under vaccum for 4 hrs. The obtained product can be stored in a dry box at room temperature for several weeks, and can be used directly.

[0040] In the following examples of the present disclosure, the main reactions can be represented by the following schemes I and II.

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EXAMPLE 1

[0041] Under N.sub.2 atmosphere, PCB waste (10 g, which comprises copolymer (HW-12 or HW-13), ink (Phthalocyanine) and plasticizer (Bis(2-ethylhexyl)phthalate, DEI-IP)) was added into acetic acid (50 ml) in a two-neck flask (250 ml). Then, the catalyst (0.5 g) and acetic anhydride (10 ml) was added. The mixture was heated to 100 C. After 56-60 hrs, the solution containg the PCB waste was transformed from sky blue into reddish brown, and the solid was white. The catalyst (catalyst A) can be, for example, Hf(O)Cl.sub.2 (Group IVB), V(O)Cl.sub.2 or V(O)(OTf).sub.2 (Group VB), MoO.sub.2C.sub.2 (Group VIB), Mn(O)(OAc) (Group VIIB), or FeCl.sub.3 (Group VIIIB). Herein, the used catalyst was MoO.sub.2Cl.sub.2.

[0042] After the reaction was completed, additional cooling step was not required. 2 ml reactant was added into 25 ml water and stirred for 10-20 mins. When there was no dyed or colored reactant, the reaction was determind to be complete. Then, the reaction mixture was slowly added into 200 ml water dropwise and smashed with a juice blender. The collected solid was added into 200 ml water, followed by stirring for 30 mins to remove acid and prevent polymer aggregation.

[0043] After collecting the solid and removing water, the clleceted solid was washed with 50 ml methanol (PCB:MeOH=1:5). After filtration, small molecules removed by the methanol was detected by TLC visualization method. After drying of the methanol solution, the obtained powders were dissolved in CDCl.sub.3, and the .sup.1H NMR thereof is shown in FIG. 1.

[0044] After removing methanol, the polymer product was dissolved with 50 ml acetic acid (product: acetic acid=1:5), followed by adding into 200 ml water. After filtering and drying, light yellow powders were obtained (weight=8.678 g, number average moleculer weight (M.sub.n)=9,805, wight average molecular weight (M.sub.w)=15,235, and polydisepersity index (PDI)=1.55). In addition, the obtained powders were dissolved in d.sub.6-DMSO, and the .sup.1H NMR spectrum thereof is shown in FIG. 2.

[0045] The results indicate that the inks can be degraded and the polymer can be acylated successfully when using the catalyst and the anhydride of the present disclosure.

EXAMPLE 2

[0046] Under N.sub.2 atmosphere, PCB waste (10 g, which comprises copolymer (HW-12 or HW-13), ink (Phthalocyanine) and plasticizer (DEHP)) was added into acetic acid (50 ml) in a two-neck flask (250 nil), and the PCB waste was smashed with a juice mixer for 30 sec. Then, the catalyst (100 mg) and CH.sub.3COCl (25 ml) was added therein, and the mixture was heated to 60-70 C. The reaction progress was detected with TLC plates, wherein 1 ml reactant was added into 25 ml water at diferent time points (6, 12, 18, 24 and 40 hrs). The solution color containing the PCB waste was transformed from sky blue into reddish brown, and the polymer was precipitated and turned into white. In this step, the catalyst A shown in Example 1 can be used. Herein, the used catalyst was V(O)Cl.sub.2.

[0047] Next, the reactant was added into water to preceed with the subsequent color removing step. First, 1 ml acetic acid and 5 g another catalyst was added in the mixture, followed by adding 5 ml 35% H.sub.2O.sub.2 after 1 hrs and stirring the mixture for 12-16 hrs. The catalyst (catalyst B) capable of using in this step can be, for exmaple, Zr(O )Cl.sub.2 or Ti(O)(acac).sub.2 (Group IVB), V(O)SO.sub.4 or V(O)(acac).sub.2 (Group VB), MoO.sub.2(acac).sub.2 (Group VIB), Mn(II)SO.sub.4 (Group VIIB), or FeSO.sub.4 (Group VIIIB). Herein, the used catalyst was V(O)SO.sub.4.

[0048] After filterring and drying, white powders can be obtained (weight=6.9170 g), and the recyling yield was determined to be 69.2%. Then, the white powders was added into 30-40 ml methanol. After filtration, the residue was dissolved in 30-40 ml acetic acid. Then, the solution was added into 100 ml deionized water. After filtrating and drying, white solid was obtained (number average molecular weight (M.sub.n)=8,605, weight average molecular weight (M.sub.w)=12,355, and polydisepersity index (PDI)=1.55), and the recyling yield was determined to be 81.3%. The obtained powders were dissolved in d.sub.6-DMSO, and the .sup.1H NMR spectrum thereof is shown in FIG. 3.

[0049] The results indicate that the polymer can be acylated successfully when using the catalyst and the anhydride of the present disclosure. In addition, the inks can be degraded by using the catalyst and the oxidant of the present disclosure.

EXAMPLE 3

[0050] Wet PCB waste (100 g, which comprises copolymer (HW-12 or HW-13), ink (Phthalocyanine) and plasticizer (DEHP)) was dissolved in acetic acid (100 ml), and the PCB waste was smashed with a juice mixer. The PCB waste was turned into dark blue when contacting the acetic acid. Then, a mixture containing 5 g catalyst and oxidant t-BuOOH (1:501:100) was heated to 55-60 C. The reaction progress was detected with TLC plates, wherein the fluorence of the ink was faded gradually. After reacting for 10-12 hrs, the reactant was turned from dark blue into reddish brown. 5 mL 35% H.sub.2O.sub.2 was added into the reaction every hour for three times. After reacting for another 12 hrs, the reatnat was turned from reddish brown into light yellow or milky white. In this step, the catalyst B shown in Example 2 can be used. Herein, the used catalyst was V(O)SO.sub.4.

[0051] Finally, the reaction mixture was added into 100 ml deionized water. After filtrating and drying, white solid can be obatained (number average molecular weight (M.sub.n)=11,767, weight average molecular weight (M.sub.w)=18,046, and polydiseperse index (PDI)=1.53), and the recyling rate was determined to be 65.6%.

[0052] The results indicate that the inks can be degraded and the pure polymer can be recylced successfully when using the catalyst and the oxidant of the present disclosure.

EXAMPLES 4-8

[0053] In the present examples, the procedures were similar to that shown in Example 2, except that the catalyst A and the catalyst B were replaced by the catalysts listed in the following Table 1.

TABLE-US-00001 TABLE 1 Catalyst A Catalyst B Example 4 MoO.sub.2Cl.sub.2 MeReO.sub.3 Example 5 ZrOCl.sub.2 V(O)(OTf).sub.2 Example 6 V(O)Cl.sub.2 FeSO.sub.4 Example 7 FeCl.sub.2 MnSO.sub.4 Example 8 CuSO.sub.4 V(O)(OAc).sub.2

[0054] As shown in the aforesaid examples, simple solvents (such as acetic acid) and simple acetylation reagents are used in the method of the present disclosure. In addition, whether the ink is degraded or not can be determined by observing the color change of the reaction mixture and solution with naked eyes.

[0055] When the catalyst of the present disclosure is used, the inks can be completely degraded into water soluable waste to meet the requirement of the environmental protection. Meanwhile, the initiators, the dyes and the plasticizer contained in PCB can be degraded, and the polymer resin can be recyled into acrylic and/or epoxy resin. Alternatively, the polymer can be acylated into acylated polymer capable of dissloving in conventional organic solvents, recyled and reused. The yield of the acrylic and/or epoxy resin (the recycling rate of PCB) can reach 60-70%, and yield of the acylated polymer (the recycling rate of PCB) can also be 60-70%. Hence, the catalyst of the present disclosure can effectively treat large amounts of inked PCB waste and the present disclosure can achieve the purpose of recyling polymers.

[0056] Although the present disclosure has been explained in relation to its embodiment, it is to be understood that many other possible modifications and variations can be made without departing from the spirit and scope of the disclosure as hereinafter claimed.