CN102513153A - Metal base ionic liquid catalyst and method for degrading polyethylene glycol terephthalate by using the same - Google Patents
Metal base ionic liquid catalyst and method for degrading polyethylene glycol terephthalate by using the same Download PDFInfo
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- CN102513153A CN102513153A CN2011102934676A CN201110293467A CN102513153A CN 102513153 A CN102513153 A CN 102513153A CN 2011102934676 A CN2011102934676 A CN 2011102934676A CN 201110293467 A CN201110293467 A CN 201110293467A CN 102513153 A CN102513153 A CN 102513153A
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Abstract
The invention discloses a metal base ionic liquid catalyst and a method for degrading polyethylene glycol terephthalate by using the same, relating to an ionic liquid catalyst and a method for degrading polyester materials. The invention solves the technical problems that the existing ionic liquid catalysts for degrading PET have large dosage and long reaction time. The metal base ionic liquid catalyst is a combination of one or several of the followings. The method comprises the following steps: weighing raw materials and adding in a reactor, heating up to 90-210 DEG C and stirring for 0.5-5 h to complete the degradation of polyethylene glycol terephthalate. The method has the advantages of mild reaction conditions, small catalyst dosage, quick reaction speed, easy recovery, and no secondary pollution, wherein the PET conversion rate reaches 60-100 % in 0.5-5 h, and the monomer yield reaches 20-90 %. The invention can be used for degradation and reclamation of waste polyethylene glycol terephthalate.
Description
Technical field
The present invention relates to the method for ionic-liquid catalyst and degraded polyester material thereof.
Background technology
The packaging material and the PET that are mainly derived from fields such as food, beverage, medical treatment as one of the main composition of " white pollution " PETG (PET) produce the waste material that produces with process.These pet wastes/many light weights of discarded object amount take up space greatly, and because the chemical inertness of PET polyester makes it be difficult to by air or microbial degradation environment caused very big influence.About the research of PET polyester renewable resources, the exploitation of novel degradation reaction catalyst is a focus and difficult point problem all the time.Ionic liquid is one type of environmentally friendly new catalyst; Receive great favor in synthetic field and catalytic field; But so far; Use reporting for work of ionic liquid-catalyzed degraded PET few in number, and catalyst type is dull, like N-methyl butyl imidazoles villaumite, N-methyl butyl imidazoles bromine salt etc.The degradation reaction consumption that these several kinds of ionic-liquid catalysts are used for PET is a length big and consuming time, and as with N-methyl butyl imidazoles villaumite catalysis PET alcoholysis, catalyst amount is greater than 10%, and reaction is more than 6 hours, and the conversion ratio of PET is less than 50%.
Summary of the invention
The present invention is that will to solve the consumption of the ionic-liquid catalyst of existing degraded PET big, the technical problem that the reaction time is long, and the Metal Substrate ionic-liquid catalyst is provided and utilizes the method for its degraded PETG.
Metal Substrate ionic-liquid catalyst of the present invention does
In or wherein several kinds combination, wherein R
1Be C
1-C
10Alkyl chain, R
2Be C
1-C
10Alkyl chain, R
3Be C
1-C
10Alkyl chain, the value of n is 1～9 integer, the value of m is 1～5 integer, M is Al
3+, Fe
2+, Ni
2+, Pb
2+, Zn
2+, Mn
2+, Mg
2+, Ca
2+, Cu
2+Or Sn
2+, X
-Be Br
-, Cl
-Or H
3CCOO
-, a
1Value be 0.1～3, a
2Value be 0.1～3, a
3Numerical value be 0.1～3, the numerical value of b is the valence electron number of M.
Utilize the method for above-mentioned Metal Substrate ionic-liquid catalyst degraded PETG to carry out according to the following steps: one, to take by weighing PETG, Metal Substrate ionic-liquid catalyst and alcohol; Wherein the quality of Metal Substrate ionic-liquid catalyst is 0.01%～9% of a PETG quality, and PETG is 1: 2.5～15 with the mass ratio of alcohol; Two, the PETG that step 1 is taken by weighing, Metal Substrate ionic-liquid catalyst and alcohol join in the reactor, and to be heated to temperature be 90 ℃～210 ℃ and stir 0.5h～5h, accomplish the degraded of PETG; Wherein the alcohol described in the step 1 is ethylene glycol, glycerine or n-butanol.
Wherein the molecular weight of the PETG in the step 1 is 1.6 * 10
4G/mol～2.6 * 10
4G/mol.
The synthetic reactional equation of the Metal Substrate ionic-liquid catalyst of degraded PETG of the present invention is following:
The ester exchange principle of utilizing of the present invention, under the catalytic action of Metal Substrate ionic-liquid catalyst, the degraded PETG.The consumption of Metal Substrate ionic-liquid catalyst is merely PETG 0.01%～9%, and the reaction time is 0.5h～5h.Method mild condition of the present invention, catalyst amount is little, and reaction speed fast (within 0.5～5h, make the conversion ratio of PET reach 60%～100%, the monomer yield reaches 20%～90%) reclaims easily non-secondary pollution.
The present invention can be used for the degraded of PETG, and the degraded of waste and old PETG is recycled.
The specific embodiment
The specific embodiment one: the Metal Substrate ionic-liquid catalyst of this embodiment does
In or wherein several kinds combination, wherein R
1Be C
1～C
10Alkyl chain, R
2Be C
1～C
10Alkyl chain, R
3Be C
1～C
10Alkyl chain, the value of n is 1～9 integer, the value of m is 1～5 integer, M is Al
3+, Fe
2+, Ni
2+, Pb
2+, Zn
2+, Mn
2+, Mg
2+, Ca
2+, Cu
2+Or Sn
2+, X
-Be Br
-, Cl
-Or H
3CCOO
-, a
1Value be 0.1～3, a
2Value be 0.1～3, a
3Numerical value be 0.1～3, the numerical value of b is the valence electron number of M.
When the Metal Substrate ionic-liquid catalyst was composition, various Metal Substrate ionic liquids were pressed arbitrarily than combination.
This embodiment utilizes the ester exchange principle, under the catalytic action of Metal Substrate ionic-liquid catalyst, and the degraded PETG.The consumption of Metal Substrate ionic-liquid catalyst is merely PETG 0.01%～9%, and the reaction time is 0.5h～5h.Method mild condition of the present invention, catalyst amount is little, and reaction speed fast (within 0.5～5h, make the conversion ratio of PET reach 60%～100%, the monomer yield reaches 20%～90%) reclaims easily non-secondary pollution.
The specific embodiment two: that this embodiment and the specific embodiment one are different is R
1Be C
3～C
7Alkyl chain.Other is identical with the specific embodiment one.
The specific embodiment three: that this embodiment and the specific embodiment one are different is R
2Be C
3～C
7Alkyl chain.Other is identical with the specific embodiment one.
The specific embodiment four: that this embodiment and the specific embodiment one are different is R
3Be C
3～C
7Alkyl chain.Other is identical with the specific embodiment one.
The specific embodiment five: this embodiment is different with the specific embodiment one or two is that the value of n is 3～6 integer.Other is identical with the specific embodiment one or two.
The specific embodiment six: this embodiment is different with the specific embodiment one or four is that the value of m is 2～4 integer.Other is identical with the specific embodiment one or four.
The specific embodiment seven: utilize the method for the specific embodiment one described Metal Substrate ionic-liquid catalyst degraded PETG to carry out according to the following steps: one, to take by weighing PETG, Metal Substrate ionic-liquid catalyst and alcohol; Wherein the quality of Metal Substrate ionic-liquid catalyst is 0.01%～9% of a PETG quality, and PETG is 1: 2.5～15 with the mass ratio of alcohol; Two, the PETG that step 1 is taken by weighing, Metal Substrate ionic-liquid catalyst and alcohol join in the reactor, and to be heated to temperature be 90 ℃～210 ℃ and stir 0.5h～5h, accomplish the degraded of PETG; Wherein the alcohol described in the step 1 is ethylene glycol, glycerine or n-butanol.
This embodiment utilizes the ester exchange principle, under the catalytic action of Metal Substrate ionic-liquid catalyst, and the degraded PETG.The consumption of Metal Substrate ionic-liquid catalyst is merely PETG 0.01%～9%, and the reaction time is 0.5h～5h.Method mild condition of the present invention, catalyst amount is little, and reaction speed fast (within 0.5～5h, make the conversion ratio of PET reach 60%～100%, the monomer yield reaches 20%～90%) reclaims easily non-secondary pollution.
The specific embodiment eight: this embodiment and the specific embodiment seven are different is that the quality of Metal Substrate ionic-liquid catalyst in the step 1 is 0.1%～5% of a PETG quality, and PETG is 1: 4～10 with the mass ratio of alcohol.Other is identical with the specific embodiment seven.
The specific embodiment nine: what this embodiment was different with the specific embodiment seven or eight is that heating-up temperature is 150 ℃～200 ℃ in the step 2, and mixing time is 1h～4h.Other is identical with the specific embodiment seven or eight.
The specific embodiment ten: this embodiment is different with one of specific embodiment seven to nine is that the molecular weight of the PETG in the step 1 is 1.6 * 10
4G/mol～2.6 * 10
4G/mol.Other is identical with one of specific embodiment seven to nine.
With following verification experimental verification effect of the present invention:
Test one: the method for utilizing Metal Substrate ionic-liquid catalyst degraded PETG of this test is carried out according to the following steps: one, taking by weighing the 1g molecular weight is 1.6 * 10
4The PETG of g/mol, 0.01g Metal Substrate ionic-liquid catalyst [Bmim] ZnBr
3With 20g ethylene glycol; Two, the PETG that step 1 is taken by weighing, Metal Substrate ionic-liquid catalyst [Bmim] ZnBr
3Join in the there-necked flask with ethylene glycol, being heated to temperature is 190 ℃ and stirring reaction 1h, accomplishes the degraded of PETG.
Material in the there-necked flask that reaction is finished filters, and with unreacted solid-state PETG isolated by filtration, with the calculating conversion ratio of weighing after these solids PET clean dry, is converted into 74.0% through what calculate PET; In the filtrating that filtration obtains, add cold water; Be placed on temperature and be in 0 ℃ the refrigerator and leave standstill 12h, monomer is separated out, and the monomer of separating out is filtered out; After washing is dry, calculating productive rate is 48.1%; And filtrating is the mixture of ethylene glycol, catalyst and water, and water and ethylene glycol are removed in distillation, just obtain the Metal Substrate ionic-liquid catalyst that reclaims.
Metal Substrate ionic-liquid catalyst [Bmim] ZnBr of this test
3Structural formula be:
The preparation method of this Metal Substrate ionic-liquid catalyst is following: at room temperature; 4.3g N-methyl-imidazole-butyl bromide and 4.4g zinc bromide joined stir 24h in the carrene, decompression distillation and vacuum drying obtain colourless viscous liquid N-methyl-butyl imidazole bromination zinc then.
Test two: the method for utilizing Metal Substrate ionic-liquid catalyst degraded PETG of this test is carried out according to the following steps: one, taking by weighing the 2g molecular weight is 1.8 * 10
4G/mol PETG, 0.0032g Metal Substrate ionic-liquid catalyst [Bmim] ZnCl
3With 20g ethylene glycol; Two, the PETG that step 1 is taken by weighing, Metal Substrate ionic-liquid catalyst [Bmim] ZnCl
3Join in the there-necked flask with ethylene glycol, being heated to temperature is 190 ℃ and stirring reaction 6h, accomplishes the degraded of PETG.
Material in the there-necked flask that reaction is finished filters, and with unreacted solid-state PETG isolated by filtration, with the calculating conversion ratio of weighing after these solids PET clean dry, is converted into 100% through what calculate PET; In the filtrating that filtration obtains, add cold water, be placed on temperature and leave standstill 12h in-1 ℃ the refrigerator, monomer is separated out; The monomer of separating out is filtered out; After washing is dry, calculating productive rate is 83.77%, and the component of filtrating is an ethylene glycol, the mixture of catalyst and water; Water and ethylene glycol are removed in distillation, just obtain the Metal Substrate ionic-liquid catalyst that reclaims.
Metal Substrate ionic-liquid catalyst [Bmim] ZnCl of this test
3Structural formula be:
The preparation method of this Metal Substrate ionic-liquid catalyst is following: at room temperature, 3.8g N-methyl-butyl imidazole chlorine and 2.3g zinc chloride are stirred 24h in carrene, and then decompression distillation and vacuum drying obtain colourless liquid [Bmim] ZnCl
3
Test three: the method for utilizing Metal Substrate ionic-liquid catalyst degraded PETG of this test is carried out according to the following steps: one, taking by weighing the 1g molecular weight is 1.9 * 10
4The PETG of g/mol, 0.0016g Metal Substrate ionic-liquid catalyst [Bmim] MnCl
3With 20g ethylene glycol; Two, the PETG that step 1 is taken by weighing, Metal Substrate ionic-liquid catalyst [Bmim] MnCl
3Join in the there-necked flask with ethylene glycol, being heated to temperature is 190 ℃ and stirring reaction 6h, accomplishes the degraded of PETG.
Material in the there-necked flask that reaction is finished filters, and with unreacted solid-state PETG isolated by filtration, with the calculating conversion ratio of weighing after these solids PET clean dry, is converted into 93.4% through what calculate PET; In the filtrating that filtration obtains, add cold water, be placed on temperature and leave standstill 12h in-2 ℃ the refrigerator, monomer is separated out; The monomer of separating out is filtered out; After washing is dry, calculating productive rate is 74.2%, and filtrating is ethylene glycol, the mixture of catalyst and water; Water and ethylene glycol are removed in distillation, just obtain the Metal Substrate ionic-liquid catalyst that reclaims.
Metal Substrate ionic-liquid catalyst [Bmim] MnCl of this test
3Structural formula be:
The preparation method of this Metal Substrate ionic-liquid catalyst is following: at room temperature, 4.3gN-methyl-butyl imidazole chlorine and 3.6g chlorination are stirred 24h suddenly in carrene, decompression distillation and vacuum drying obtain light green solid [Bmim] MnCl then
3
Test four: the method for utilizing Metal Substrate ionic-liquid catalyst degraded PETG of this test is carried out according to the following steps: one, taking by weighing the 1g molecular weight is 1.9 * 10
4The PETG of g/mol, 0.05g Metal Substrate ionic-liquid catalyst [Bmim] ZnCl
3With 20g ethylene glycol; Two, the PETG that step 1 is taken by weighing, Metal Substrate ionic-liquid catalyst [Bmim] ZnCl
3Join in the there-necked flask with ethylene glycol, being heated to temperature is 180 ℃ and stirring reaction 2h, accomplishes the degraded of PETG.
Material in the there-necked flask that reaction is finished filters, and with unreacted solid-state PETG isolated by filtration, with the calculating conversion ratio of weighing after these solids PET clean dry, is converted into 61.7% through what calculate PET; In the filtrating that filtration obtains, add cold water; Be placed on temperature and leave standstill more than the 10h, have monomeric substance to separate out, the monomer of separating out is filtered out in-10 ℃-0 ℃ the refrigerator; After washing is dry, calculating productive rate is 46.5%; And filtrating is the mixture of ethylene glycol, catalyst and water, and water and ethylene glycol are removed in distillation, just obtain the Metal Substrate ionic-liquid catalyst that reclaims.
Metal Substrate ionic-liquid catalyst [Bmim] ZnCl of this test
3Structural formula be:
The preparation method of this Metal Substrate ionic-liquid catalyst is identical with test two.
Test five: the method for utilizing Metal Substrate ionic-liquid catalyst degraded PETG of this test is carried out according to the following steps: one, taking by weighing the 1g molecular weight is 2.6 * 10
4The PETG of g/mol, 0.0125g Metal Substrate ionic-liquid catalyst [Bmim] MnCl
3With 20g ethylene glycol; Two, the PETG that step 1 is taken by weighing, Metal Substrate ionic-liquid catalyst [Bmim] MnCl
3Join in the there-necked flask with ethylene glycol, being heated to temperature is 190 ℃ and stirring reaction 2h, accomplishes the degraded of PETG.
Material in the there-necked flask that reaction is finished filters, and with unreacted solid-state PETG isolated by filtration, with the calculating conversion ratio of weighing after these solids PET clean dry, is converted into 100% through what calculate PET; In the filtrating that filtration obtains, add cold water; Be placed on temperature and leave standstill 15h in-3 ℃ the refrigerator; Monomeric substance is separated out, and filtering to isolate monomer once more and washing dry calculating productive rate is 82.5%, and filtrating is the mixture of ethylene glycol, catalyst and water; Water and ethylene glycol are removed in distillation, just obtain the Metal Substrate ionic-liquid catalyst that reclaims.
Metal Substrate ionic-liquid catalyst [Bmim] MnCl of this test
3Structural formula be:
The preparation method of this Metal Substrate ionic-liquid catalyst is identical with the method for testing in three.
Test six: the method for utilizing Metal Substrate ionic-liquid catalyst degraded PETG of this test is carried out according to the following steps: one, taking by weighing the 1g molecular weight is 2.4 * 10
4The PETG of g/mol, 0.0125g Metal Substrate ionic-liquid catalyst [Bmim] FeCl
3With 20g ethylene glycol; Two, the PETG that step 1 is taken by weighing, Metal Substrate ionic-liquid catalyst [Bmim] FeCl
3Join in the there-necked flask with ethylene glycol, being heated to temperature is 190 ℃ and stirring reaction 2h, accomplishes the degraded of PETG.
Material in the there-necked flask that reaction is finished filters, and with unreacted solid-state PETG isolated by filtration, with the calculating conversion ratio of weighing after these solids PET clean dry, is converted into 95.5% through what calculate PET; In the filtrating that filtration obtains, add cold water, be placed on temperature and leave standstill 12h in-10 ℃ the refrigerator, monomeric substance is separated out.Filtering to isolate monomer once more and washing dry calculating productive rate is 74.0%, and the component of filtrating is an ethylene glycol, the mixture of catalyst and water, and water and ethylene glycol are removed in distillation, just obtain the Metal Substrate ionic-liquid catalyst that reclaims.
Metal Substrate ionic-liquid catalyst [Bmim] FeCl of this test
3Structural formula be:
The preparation method of this Metal Substrate ionic-liquid catalyst is following: at room temperature, 0.54g N-methyl-butyl imidazole chlorine and 0.61g frerrous chloride are stirred 24h at 80 ℃, vacuum drying gets kermesinus [Bmim] FeCl
3
Test seven: the method for utilizing Metal Substrate ionic-liquid catalyst degraded PETG of this test is carried out according to the following steps: one, taking by weighing the 1g molecular weight is 2.4 * 10
4The PETG of g/mol, 0.05g Metal Substrate ionic-liquid catalyst [Bmim] PbBr
3With 20g ethylene glycol; Two, the PETG that step 1 is taken by weighing, Metal Substrate ionic-liquid catalyst [Bmim] PbBr
3Join in the there-necked flask with ethylene glycol, being heated to temperature is 190 ℃ and stirring reaction 2h, accomplishes the degraded of PETG.
Material in the there-necked flask that reaction is finished filters, and with unreacted solid-state PETG isolated by filtration, with the calculating conversion ratio of weighing after these solids PET clean dry, is converted into 83.0% through what calculate PET; In the filtrating that filtration obtains, add cold water, be placed on temperature and leave standstill 15h in-6 ℃ the refrigerator, monomeric substance is separated out.Filtering to isolate monomer once more and washing dry calculating productive rate is 63.3%, and filtrating is the mixture of ethylene glycol, catalyst and water, and water and ethylene glycol are removed in distillation, just obtain the Metal Substrate ionic-liquid catalyst that reclaims.
Metal Substrate ionic-liquid catalyst [Bmim] PbBr of this test
3Structural formula be:
The preparation method of this Metal Substrate ionic-liquid catalyst is following: at room temperature, 0.85g N-methyl-imidazole-butyl bromide and 0.50g lead bromide are joined in the container, be warming up to 90 ℃ and stir 24h, and then vacuum drying gets [Bmim] PbBr
3
Test eight: the method for utilizing Metal Substrate ionic-liquid catalyst degraded PETG of this test is carried out according to the following steps: one, taking by weighing the 1g molecular weight is 2.2 * 10
4The PETG of g/mol, 0.01g Metal Substrate ionic-liquid catalyst [Emim] ZnBr
3With 20g ethylene glycol; Two, the PETG that step 1 is taken by weighing, Metal Substrate ionic-liquid catalyst [Emim] ZnBr
3Join in the there-necked flask with ethylene glycol, being heated to temperature is 190 ℃ and stirring reaction 1h, accomplishes the degraded of PETG.
Material in the there-necked flask that reaction is finished filters, and with unreacted solid-state PETG isolated by filtration, with the calculating conversion ratio of weighing after these solids PET clean dry, is converted into 40.0% through what calculate PET; In the filtrating that filtration obtains, add cold water, be placed on temperature and leave standstill 12h in-8 ℃ the refrigerator, monomeric substance is separated out.Filtering to isolate monomer once more and washing dry calculating productive rate is 28.3%, and filtrating is the mixture of ethylene glycol, catalyst and water, and water and ethylene glycol are removed in distillation, just obtain the Metal Substrate ionic-liquid catalyst that reclaims.
Metal Substrate ionic-liquid catalyst [Emim] ZnBr of this test
3Structural formula be:
The preparation method of this Metal Substrate ionic-liquid catalyst: at room temperature, 3.1gN-methyl-ethyl imidazol(e) bromine and 3.7g zinc bromide joined stir 24h in the carrene, obtain [Emim] ZnBr
3
Test nine: the method for utilizing Metal Substrate ionic-liquid catalyst degraded PETG of this test is carried out according to the following steps: one, taking by weighing the 1g molecular weight is 1.9 * 10
4The PETG of g/mol, 0.01g Metal Substrate ionic-liquid catalyst [Pmim] ZnCl
3With 20g ethylene glycol; Two, the PETG that step 1 is taken by weighing, Metal Substrate ionic-liquid catalyst [Pmim] ZnCl
3Join in the there-necked flask with ethylene glycol, being heated to temperature is 190 ℃ and stirring reaction 1h, accomplishes the degraded of PETG.
Material in the there-necked flask that reaction is finished filters, and with unreacted solid-state PETG isolated by filtration, with the calculating conversion ratio of weighing after these solids PET clean dry, is converted into 49.3% through what calculate PET; In the filtrating that filtration obtains, add cold water, be placed on temperature and leave standstill 15h in-9 ℃ the refrigerator, monomeric substance is separated out.Filtering to isolate monomer once more and washing dry calculating productive rate is 41.6%, and filtrating is the mixture of ethylene glycol, catalyst and water, and water and ethylene glycol are removed in distillation, just obtain the Metal Substrate ionic-liquid catalyst that reclaims.
Metal Substrate ionic-liquid catalyst [Pmim] ZnCl of this test
3Structural formula be:
The preparation method of this Metal Substrate ionic-liquid catalyst is following: at room temperature, 3.0gN-methyl-amyl group imidazoles chlorine and 2.2g zinc chloride are stirred 24h in carrene, decompression distillation and vacuum drying obtain [Pmim] ZnCl
3
Test ten: the method for utilizing Metal Substrate ionic-liquid catalyst degraded PETG of this test is carried out according to the following steps: one, taking by weighing the 1g molecular weight is 1.9 * 10
4The PETG of g/mol, 0.01g Metal Substrate ionic-liquid catalyst [Omim] ZnCl
2Br and 20g ethylene glycol; Two, the PETG that step 1 is taken by weighing, Metal Substrate ionic-liquid catalyst [Omim] ZnCl
2Br and ethylene glycol join in the there-necked flask, and being heated to temperature is 190 ℃ and stirring reaction 1h, accomplishes the degraded of PETG.
Material in the there-necked flask that reaction is finished filters, and with unreacted solid-state PETG isolated by filtration, with the calculating conversion ratio of weighing after these solids PET clean dry, is converted into 46.8% through what calculate PET; In the filtrating that filtration obtains, add cold water, be placed on temperature and leave standstill 12h in-10 ℃ the refrigerator, monomeric substance is separated out.Filtering to isolate monomer once more and washing dry calculating productive rate is 36.4%, and filtrating is the mixture of ethylene glycol, catalyst and water, and water and ethylene glycol are removed in distillation, just obtain the Metal Substrate ionic-liquid catalyst that reclaims.
Metal Substrate ionic-liquid catalyst [Omim] ZnCl of this test
2The structural formula of Br is:
The preparation method of this Metal Substrate ionic-liquid catalyst is following: under the room temperature 3.7gN-methyl-octyl group imidazoles bromine and 1.9g zinc chloride (1.8241g) joined and stir 24h in the carrene, decompression distillation and vacuum drying obtain [Omim] ZnCl
2Br.
Test 11: the method for utilizing Metal Substrate ionic-liquid catalyst degraded PETG of this test is carried out according to the following steps: one, taking by weighing the 1g molecular weight is 2.2 * 10
4The PETG of g/mol, 0.05g Metal Substrate ionic-liquid catalyst [Bmim] Mn (Ac)
3With 20g ethylene glycol; Two, the PETG that step 1 is taken by weighing, Metal Substrate ionic-liquid catalyst [Bmim] Mn (Ac)
3Join in the there-necked flask with ethylene glycol, being heated to temperature is 190 ℃ and stirring reaction 2h, accomplishes the degraded of PETG.
Material in the there-necked flask that reaction is finished filters, and with unreacted solid-state PETG isolated by filtration, with the calculating conversion ratio of weighing after these solids PET clean dry, is converted into 100% through what calculate PET; In the filtrating that filtration obtains, add cold water, be placed on temperature and leave standstill 12h in-10 ℃ the refrigerator, monomeric substance is separated out.Filtering to isolate monomer once more and washing dry calculating productive rate is 75.4%, and the component of filtrating is the mixture of ethylene glycol, catalyst and water, and water and ethylene glycol are removed in distillation, just obtain the Metal Substrate ionic-liquid catalyst that reclaims.
Metal Substrate ionic-liquid catalyst [Bmim] Mn (Ac) of this test
3Structural formula be:
The preparation method of this Metal Substrate ionic-liquid catalyst is following: at room temperature 5.2gN-methyl-imidazole-butyl bromide and 2.4g sodium acetate were reacted in carrene 48 hours, filtering also, decompression distillation at first obtains N-methyl-butyl imidazole acetate.N-methyl-butyl imidazole acetate stirs 24h with the manganese acetate of amount of substance such as grade in carrene, decompression distillation and vacuum drying obtain [Bmim] Mn (Ac)
3
Claims (10)
1. the Metal Substrate ionic-liquid catalyst is characterized in that the Metal Substrate ionic-liquid catalyst does
In or wherein several kinds combination, wherein R
1Be C
1～C
10Alkyl chain, R
2Be C
1～C
10Alkyl chain, R
3Be C
1～C
10Alkyl chain, the value of n is 1～9 integer, the value of m is 1～5 integer, M is Al
3+, Fe
2+, Ni
2+, Pb
2+, Zn
2+, Mn
2+, Mg
2+, Ca
2+, Cu
2+Or Sn
2+, X
-Be Br
-, Cl
-Or H
3CCOO
-, a
1Value be 0.1～3, a
2Value be 0.1～3, a
3Numerical value be 0.1～3, the numerical value of b is the valence electron number of M.
2. Metal Substrate ionic-liquid catalyst according to claim 1 is characterized in that R
1Be C
3～C
7Alkyl chain.
3. Metal Substrate ionic-liquid catalyst according to claim 1 is characterized in that R
2Be C
3～C
7Alkyl chain.
4. Metal Substrate ionic-liquid catalyst according to claim 1 is characterized in that R
3Be C
3～C
7Alkyl chain.
5. Metal Substrate ionic-liquid catalyst according to claim 1 and 2, the value that it is characterized in that n are 3～6 integers.
6. according to claim 1 or 4 described Metal Substrate ionic-liquid catalysts, the value that it is characterized in that m is 2～4 integer.
7. utilize the method for the described Metal Substrate ionic-liquid catalyst degraded of claim 1 PETG; It is characterized in that utilizing the method for Metal Substrate ionic-liquid catalyst degraded PETG to carry out according to the following steps: one, to take by weighing PETG, Metal Substrate ionic-liquid catalyst and alcohol; Wherein the quality of Metal Substrate ionic-liquid catalyst is 0.01%～9% of a PETG quality, and PETG is 1: 2.5～15 with the mass ratio of alcohol; Two, the PETG that step 1 is taken by weighing, Metal Substrate ionic-liquid catalyst and alcohol join in the reactor, and to be heated to temperature be 90 ℃～210 ℃ and stir 0.5h～5h, accomplish the degraded of PETG; Wherein the alcohol described in the step 1 is ethylene glycol, glycerine or n-butanol.
8. the method for utilizing Metal Substrate ionic-liquid catalyst degraded PETG according to claim 7; The quality that it is characterized in that Metal Substrate ionic-liquid catalyst in the step 1 is 0.1%～5% of a PETG quality, and PETG is 1: 4～10 with the mass ratio of alcohol.
9. according to claim 7 or the 8 described methods of utilizing Metal Substrate ionic-liquid catalyst degraded PETG, it is characterized in that heating-up temperature is 150 ℃～200 ℃ in the step 2, mixing time is 1h～4h.
10. according to claim 7 or the 8 described methods of utilizing Metal Substrate ionic-liquid catalyst degraded PETG, the molecular weight that it is characterized in that the PETG in the step 1 is 1.6 * 10
4G/mol～2.6 * 10
4G/mol.
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| CN105254503A (en) * | 2015-10-30 | 2016-01-20 | 青岛科技大学 | Preparation method of dioctyl terephthalate |
| CN106065068A (en) * | 2016-07-27 | 2016-11-02 | 安徽泰达新材料股份有限公司 | Pure polyester used for powder coating and preparation method thereof |
| CN106380581A (en) * | 2016-08-26 | 2017-02-08 | 安徽泰达新材料股份有限公司 | Polyester resin for indoor powder paint and preparation method thereof |
| CN107721917A (en) * | 2017-10-16 | 2018-02-23 | 河南理工大学 | A kind of green synthesis method of polysubstituted nicotinate compound |
| CN108178768A (en) * | 2017-12-27 | 2018-06-19 | 商丘师范学院 | A kind of preparation method and application of dichloro two (1- butyl imidazoles) zinc catalyst |
| CN109651255A (en) * | 2018-10-31 | 2019-04-19 | 浙江工业大学 | A kind of glyoxaline ion liquid and its preparation and the application in vitamin e acetate synthesizes |
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| CN105254503A (en) * | 2015-10-30 | 2016-01-20 | 青岛科技大学 | Preparation method of dioctyl terephthalate |
| CN105254503B (en) * | 2015-10-30 | 2017-04-19 | 青岛科技大学 | Preparation method of dioctyl terephthalate |
| CN106065068A (en) * | 2016-07-27 | 2016-11-02 | 安徽泰达新材料股份有限公司 | Pure polyester used for powder coating and preparation method thereof |
| CN106065068B (en) * | 2016-07-27 | 2017-10-27 | 安徽泰达新材料股份有限公司 | Powdery paints pure polyester and preparation method thereof |
| CN106380581A (en) * | 2016-08-26 | 2017-02-08 | 安徽泰达新材料股份有限公司 | Polyester resin for indoor powder paint and preparation method thereof |
| CN106380581B (en) * | 2016-08-26 | 2018-04-06 | 安徽泰达新材料股份有限公司 | Indoor polyester resin for powder coating and preparation method thereof |
| CN107721917A (en) * | 2017-10-16 | 2018-02-23 | 河南理工大学 | A kind of green synthesis method of polysubstituted nicotinate compound |
| CN107721917B (en) * | 2017-10-16 | 2020-07-10 | 河南理工大学 | Green synthesis method of polysubstituted nicotinate compound |
| CN108178768A (en) * | 2017-12-27 | 2018-06-19 | 商丘师范学院 | A kind of preparation method and application of dichloro two (1- butyl imidazoles) zinc catalyst |
| CN108178768B (en) * | 2017-12-27 | 2019-11-19 | 商丘师范学院 | A kind of preparation method and application of dichloro two (1- butyl imidazole) zinc catalyst |
| CN109651255A (en) * | 2018-10-31 | 2019-04-19 | 浙江工业大学 | A kind of glyoxaline ion liquid and its preparation and the application in vitamin e acetate synthesizes |
| CN109651255B (en) * | 2018-10-31 | 2020-10-27 | 浙江工业大学 | Imidazole ionic liquid, preparation thereof and application thereof in synthesis of vitamin E acetate |
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