CN1067715C - Still cleaning agent and its preparing method and use - Google Patents
Still cleaning agent and its preparing method and use Download PDFInfo
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- CN1067715C CN1067715C CN96109549A CN96109549A CN1067715C CN 1067715 C CN1067715 C CN 1067715C CN 96109549 A CN96109549 A CN 96109549A CN 96109549 A CN96109549 A CN 96109549A CN 1067715 C CN1067715 C CN 1067715C
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- cleaning agent
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Abstract
The present invention relates to a kettle cleaning agent and a preparing method and purposes thereof. The kettle cleaning agent is a prepolymer of polyester in aryl group, and the constitutional formula of the present invention is shown on the right. The prepolymer mainly comprises dimer (n=2), and also comprises trimer (n=3) and tetramer (n=4). The kettle cleaning agent can be prepared by a monomer method or a polymerisate method. The kettle cleaning agent of the present invention is especially suitable for cleaning kettles which are used for producing polyester (such as PET, PBT, etc.) and polyester elastic bodies (such as PET-PTMG, PBT-PTMG, etc.). The present invention has the advantages of simple compounding method, strong kettle cleaning capability, rapid and convenient kettle cleaning, repeated use, etc. A plurality of factories which produce polyester can be found in China at present, so the kettle cleaning agent has low cost, convenient preparation and easy popularization.
Description
The present invention relates to a kind of method of cleaning the reactor of macromolecular compound, particularly a kind of method of cleaning polycondensation macromolecular compound reactor.
For a long time, produce the aromatic polyester family macromolecule with melt-polycondensation with vertical retort, as PET, PBT and production polyester-polyethers polyester elastomer, as being hard section with PET, serve as hard section for soft section PET-PTMG or with PBT, be soft section PBT-PTMG etc. with polytetramethylene ether that with polytetramethylene ether (PTMG) react the later stage, product viscosity is very high, mobile very poor, sticking wall, sticking agitator strengthen with viscosity, and situation is serious further.The PET resin properties viscosity number of common viscosity is 0.65-0.67, and full-bodied PET resin properties viscosity number is 0.8, and PBT resin properties viscosity number is greater than 1.0, and the polyester elastomer intrinsic viscosity is then greater than 1.2.Above-mentioned height glues product, after reaction is finished, generally adopts in the bottom discharge of rare gas element (as nitrogen) pressure, and viscosity is big more, residue in and expect in the still that body is many more, for polyester, has 10% residual material approximately, for polyester elastomer, residual material reaches 15%-30%, and the cleaning of kettle is an a great problem for this reason.At present the method that adopts be that machinery cleans or solvent wash, and all time-consuming, the effort of these two kinds of methods is cleaned untotally, and solvent is washed cost height, pollution greatly.A kind of clean-out system of removing the remaining material of polyester was disclosed as RD344080 in 1993, but owing to adopt N-Methyl pyrrolidone reagent, complicated operation, contaminative is big.JP05295393 disclose when high temperature adopt amine and alcohol mixture as clean-out system, but during to continuous production, will influence the color of product.EP638354 discloses the cleaning of carrying out reactor with the multiaxis mixing tank, and this mechanical cleaning way is difficult to remove the residue of clear still inwall.
The present invention has overcome and adopts machinery to clean and time-consuming during the solvent cleaning polymeric kettle, effort, heavy-polluted shortcoming, saves time the method for the reactor of labour-saving cleaning aromatic polyester family macromolecule compound and provide a kind of.
According to the same or similar principle that best mutual solubility is arranged of structure, utilize polyester to give aggressiveness and polyester type polymer (polyester, polyester elastomer) has same or analogous structure, make and be cleaned polyester in cleaning agent and the still or the remaining material of polyester elastomer has good avidity, behind the cleaning agent heating and melting, the remnant of full-bodied polyester or polyester elastomer is dispersed in the cleaning agent very soon, because polyester gives the viscosity very little ([η]＜0.4) of aggressiveness, good fluidity can be emitted kettle smoothly with the remnant of still inwall and discharge port.
Cleaning agent of the present invention is that aromatic polyester gives aggressiveness, has structural formula to be:
The described aggressiveness that gives is dimer (n=2), the tripolymer (mixture of the n=3 or the tetramer (n=4) and any component and content.
The preparation route of cleaning agent of the present invention comprises two kinds of methods of simplex method and polymeric method.
1, simplex method
Initiator is dimethyl terephthalate (DMT) (DMT) and dibasic alcohol, generally adopts the low ethylene glycol of price, and starting material and consumption thereof see Table 1.
Table 1, monomer legal system cleaning agent raw material and consumption (weight part)
| Material name | Consumption |
| Dimethyl terephthalate (DMT) (DMT) | 100 parts |
| Ethylene glycol | 65-85 part |
| Catalyzer | 0.065-0.095 part |
Above-mentioned catalyzer is the acetate of manganese, cobalt, magnesium, calcium etc.
Press table 1 prescription, in reactor, drop into DMT, ethylene glycol and catalyzer, feed nitrogen, begin to be heated to 140 ℃, treat the DMT fusion after, begin to stir, about 180 ℃, methyl alcohol steams, and keeps 180 ℃～220 ℃, and preferred temperature is 180-200 ℃, reacted 1.5-3 hour, after making the quantity of methyl alcohol that steams reach the 80-90% of theoretical amount, get final product stopped reaction, obtain white cured shape cleaning agent, melt temperature: 180 ℃-200 ℃.
2, polymeric method
Utilize clean useless PET polyester material, as useless film, silk, fiber, bottle, polyester non-woven fabric etc. all can, must be before using through fragmentation and strictness drying.Starting material and consumption see Table 2.
Table 2, polymeric method are produced the starting material and the consumption of cleaning agent
| Material name | Consumption |
| PET[η]=0.65 ± 0.01 deciliter/gram | 100 parts |
| Ethylene glycol | 65-85 part |
| Catalyzer | 0.065-0.095 part |
Above-mentioned catalyzer is the acetate of manganese, cobalt, zinc, calcium etc.
Press table 2 prescription, in reactor, drop into PET, ethylene glycol and catalyzer respectively, feed nitrogen, heating refluxes ethylene glycol, at 200-250 ℃, is preferably 230-250 ℃, after treating the PET complete alcoholysis, continue again to stir to get final product termination reaction in 0.5-1 hour, obtain white cured shape cleaning agent.
Adopt cleaning agent of the present invention can clean the kettle of producing polyester or polyester elastomer easy, apace.After the above-mentioned kettle discharging, input is equivalent to produce the cleaning agent of polyester or polyester elastomer total amount 30-70% (weight percentage), after the complete fusion of cleaning agent, stir half an hour, then can make the polymer that sticks on reactor inwall and the agitator be dispersed in the cleaning agent very soon, after cleaning agent was emitted, kettle was clean, bright, no remnant, and cleaning agent can use repeatedly for several times.
Embodiment 1,
In 500 liters of reactors, drop into 150 kilograms of DMT, 110 kilograms of ethylene glycol; and 0.06 kilogram of manganese acetate, under nitrogen protection, heat DMT fusing back (about 140 ℃); begin to stir, temperature rises to 180 ℃, begins to have methyl alcohol to steam; at 180-220 ℃, reacted 1.5 hours, when treating that the Methanol Recovery amount is about 40 kilograms; stopped reaction; obtain about 220 kilograms and give aggressiveness, emit kettle, still to be washed is used.Embodiment 2,
In 500 liters of reactors, drop into 150 kilograms of DMT, 110 kilograms of ethylene glycol; and 0.06 kilogram of manganese acetate, under nitrogen protection, heat DMT fusing back (about 140 ℃); begin to stir, temperature rises to 180 ℃, begins to have methyl alcohol to steam; at 180-200 ℃, reacted 2.5 hours, when treating that the Methanol Recovery amount is about 40 kilograms; stopped reaction; obtain about 220 kilograms and give aggressiveness, emit kettle, still to be washed is used.Embodiment 3,
Polyester waste silks is cut off; oven dry in 150 liters of reactors, drops into 40 kilograms of above-mentioned waste silks; 14 kilograms of ethylene glycol and 0.02 kilogram of manganese acetate; heat under nitrogen protection, ethylene glycol is refluxed, polyester waste silks alcoholysis temperature is at 200-250 ℃; after treating that waste silk all dissolves; continue to stir 1 hour, stopped reaction obtains about 50 kilograms of polyester and gives aggressiveness.Embodiment 4,
Polyester waste silks is cut off; oven dry in 150 liters of reactors, drops into 40 kilograms of above-mentioned waste silks; 14 kilograms of ethylene glycol and 0.02 kilogram of manganese acetate; heat under nitrogen protection, ethylene glycol is refluxed, the alcoholysis temperature is at 230-250 ℃; after treating that waste silk all dissolves; continue to stir 0.5 hour, stopped reaction obtains about 50 kilograms of polyester and gives aggressiveness.Embodiment 5,
Produce 110 kilograms of PET resins with 200 liters of reactors, after the discharging, 50 kilograms of the cleaning agents of adding embodiment 2 preparations feed nitrogen, and the still temperature is 250 ℃ this moment, and cleaning agent melts gradually, stirs half an hour, emits cleaning agent, and reactor cleans up.Embodiment 6,
In 700 liter reactors, produce 350 kilograms of PBT resins, after the discharging, add and press 200 kilograms of the cleaning agents that embodiment 4 prepares, wash still by embodiment 5 described programs.After emitting cleaning agent, kettle is clean.Embodiment 7
Producing 250 kilograms in 700 liter reactors is hard section with PBT, being 1000 polytetramethylene ether (PTMG) with molecular weight is soft section polyester elastomer PBT-PTMG, firmly, the soft chain segment weight ratio is 40: 60, after discharging is finished in reaction, add and press 150 kilograms of the cleaning agents that embodiment 1 prepares, wash still by embodiment 5 described programs, emit cleaning agent after, kettle is clean.Embodiment 8
Producing 80 kilograms in 200 liter reactors is hard section with PBT, being 2000 polytetramethylene ether (PTMG) with molecular weight is soft section polyester elastomer PET-PTMG, firmly, the soft chain segment weight ratio is 25: 75, after discharging is finished in reaction, add and press 50 kilograms of the cleaning agents that embodiment 3 prepares, wash still by embodiment 5 described programs, emit cleaning agent after, kettle is clean.Embodiment 9,
Producing 200 kilograms in 500 liter reactors is hard section with PET, being 4000 polyglycol ether (PEG) with molecular weight is soft section polyester elastomer PET-PEG, firmly, the soft chain segment weight ratio is 40: 60, after discharging is finished in reaction, add and press 130 kilograms of the cleaning agents that embodiment 4 prepares, wash still by embodiment 5 described programs, emit cleaning agent after, kettle is clean.Embodiment 10,
Producing 150 kilograms in 300 liter reactors is hard section with PET, being 1000 polypropylene glycol ether (PPG) with molecular weight is soft section polyester elastomer PET-PPG, firmly, the soft chain segment weight ratio is 35: 65, after discharging is finished in reaction, add and press 90 kilograms of the cleaning agents that embodiment 2 prepares, wash still by embodiment 5 described programs, emit cleaning agent after, kettle is clean.
Claims (1)
1, a kind of method of producing polyester or polyester elastomer reactor of cleaning, it is characterized in that after the kettle discharging, input is equivalent to produce the cleaning agent of polyester or polyester elastomer total amount 30-70%, after the complete fusion of cleaning agent, stirred 0.5 hour, emit cleaning agent, kettle does not have resistates, and above-mentioned cleaning agent is that the following aromatic polyester of structural formula gives aggressiveness:
N=2 in the formula, 3 or 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96109549A CN1067715C (en) | 1996-08-29 | 1996-08-29 | Still cleaning agent and its preparing method and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96109549A CN1067715C (en) | 1996-08-29 | 1996-08-29 | Still cleaning agent and its preparing method and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1175626A CN1175626A (en) | 1998-03-11 |
| CN1067715C true CN1067715C (en) | 2001-06-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96109549A Expired - Fee Related CN1067715C (en) | 1996-08-29 | 1996-08-29 | Still cleaning agent and its preparing method and use |
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| Country | Link |
|---|---|
| CN (1) | CN1067715C (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047510A (en) * | 1989-05-24 | 1990-12-05 | 阿莫科公司 | The preparation of polyethylene terephthalate |
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1996
- 1996-08-29 CN CN96109549A patent/CN1067715C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047510A (en) * | 1989-05-24 | 1990-12-05 | 阿莫科公司 | The preparation of polyethylene terephthalate |
Non-Patent Citations (1)
| Title |
|---|
| 《基础有机化学》1994.6.1 邢其毅，徐瑞秋，高教出版社 * |
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| Publication number | Publication date |
|---|---|
| CN1175626A (en) | 1998-03-11 |
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