CN1032347A - The preparation method of modified polyester resin - Google Patents
The preparation method of modified polyester resin Download PDFInfo
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- CN1032347A CN1032347A CN 88105103 CN88105103A CN1032347A CN 1032347 A CN1032347 A CN 1032347A CN 88105103 CN88105103 CN 88105103 CN 88105103 A CN88105103 A CN 88105103A CN 1032347 A CN1032347 A CN 1032347A
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- China
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- reaction
- catalyzer
- polyester resin
- stir
- make
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- Phenolic Resins Or Amino Resins (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
A kind of preparation method of modified polyester resin, it is to make vibrin with cobalt manganese residue, polyester residue, linking agent and catalyzer, make resol with phenol, formaldehyde, catalyzer and alkali, and make modified polyester resin with resol, vibrin and infiltration thinner.Modified polyester resin with this method production, it is a kind of tackiness agent that is specially adapted to manufacture magnesia carbon brick, it has not only that cost is low, cohesive force is strong, good dispersity, do not absorb water, easy long storage, and consumption is few in use, need not to add deleterious urotropine firming agent and other subsidiary material, and improved the quality of magnesia carbon brick.
Description
The present invention relates to a kind of preparation method of modified poly ester.With the resin of this method preparation, be a kind of tackiness agent that is specially adapted to manufacture magnesia carbon brick.
So far, the tackiness agent that is used to manufacture magnesia carbon brick has multiple, if any tar-bitumen, phenolic resin, modified phenolic resin etc.But these tackiness agent ubiquities have weak points such as cost height, expensive, the easy suction of price, cohesive force be relatively poor.In order to improve cohesive force, generally need add a certain amount of deleterious urotropine in use as solidifying agent, it is contaminate environment not only, and directly endangers operator's health.
The manufacture method that the purpose of this invention is to provide a kind of modified poly ester resin.And with having of producing of this method cost is low, cohesive force strong, good dispersity, do not absorb water, easy long storage.And usage quantity is few.Need not to add the modified polyester resin of deleterious urotropine and other subsidiary material.
The present invention realizes that the technical solution of above-mentioned purpose is: with cobalt manganese residue, polyester residue that petrochemical enterprise discharged is main raw material, produces vibrin.Mainly utilize still residual in contained various ester classes.The contained major ingredient of its cobalt manganese residue is roughly as follows:
CH
3-COOC-C
6H
4-COOCH
2-C
6H
4-COOCH
350%
CH
3-C
6H
4-COOCH
2-C
6H
4-COOCH
315%
DMT isomer 15%
All the other are:
1, the fragrant nuclear compound of the list of simple function group;
2, the ester compound of many virtue nuclears;
3, lactone, as the adjacent chomene ketone derivatives of benzo;
4, biphenyl derivatives;
5, benzophenone;
The contained major ingredient of its polyester residue is roughly as follows:
1, ethylene glycol terephthalate 50%
2, ethylene glycol 35%
3, Diethylene Glycol 12%
In order to produce vibrin with certain degree of crosslinking.And reclaim a certain amount of methyl alcohol and ethylene glycol.With cobalt manganese residue, polyesterols residue, linking agent, catalyzer by weight: 0.6: 0.4: 0.03: 0.0005 drops in the reactor, and heats, stirs, and makes it carry out transesterification reaction and polycondensation.When carrying out transesterification reaction, polycondensation, carry out normal vacuum fractionation.The methyl alcohol that generates in the transesterify process constantly distillates.When no methyl alcohol distillated, then transesterification reaction stopped.Its transesterification reaction meets following formula substantially:
Transesterification reaction at the end begins decompression and changes polycondensation over to, and the ethylene glycol that generates in polycondensation process constantly distillates, and when no ethylene glycol distillates, the reometer tabular value rises, when the stirrer rotating speed reduces, and then polycondensation termination.Its polycondensation meets following formula substantially:
After reaction finishes, stop heating, stir, remove vacuum, emit material, make its cooling, pulverize after the curing.The linking agent that adopts is a polyvalent alcohol.Glycerol preferably.Catalyzer is a plumbous oxide, preferably the yellow lead oxide.
With phenol, formaldehyde, catalyzer is that main raw material is produced liquid phenolic resin.In order to reduce cost, its phenol preferably adopts technical phenol.Its catalyzer is an acids, preferably hydrochloric acid.Its technological process is that at first with technical phenol, formaldehyde, catalyzer by weight: 0.5-0.7: 0.30-0.40: 0.02-0.003 drops in the reactor, and heated and stirred, under reduced pressure, makes it carry out polyreaction.Temperature of reaction is 110 ℃ ± 10 ℃, and reaction pressure is vacuum tightness 500-650mmHg, after the reaction beginning, stops heating.Keep reaction for some time.Question response liquid is behind transparent, the no bubble with the alkali neutralization, when the PH=7 falling ball viscosity is 60-80 during second, stops to stir, and removes vacuum, emits material.In order to reduce cost, used alkali can be industrial soda.
With the above-mentioned liquid phenolic resin that makes, polyester resin powder and infiltration thinner by weight: 0.2-0.3: 0.6-0.7: 0.2-0.3 puts in the reactor successively, and heat, stir, make it permeate dilution, become homogeneous phase until reaction mass, falling ball viscosity be 100-120 during second till, products obtained therefrom is modified polyester resin.Used infiltration thinner is alcohols, preferably glycol ether.The infiltration dilution is to carry out under 100 ℃ ± 5 ℃ condition.
Advantage of the present invention is: one, owing to adopted cobalt manganese residue, the polyester residue is the method for main material production vibrin, not only economical and effective has reasonably been utilized cobalt manganese residue polyester residue, and prevented the pollution that these wastes bring to environment, and eliminated the three wastes up hill and dale, regained a certain amount of methyl alcohol and ethylene glycol simultaneously.Two,, and vibrin is carried out modification with it owing to utilized industrial acids to produce liquid phenolic resin.Improve the cohesive force of polyester widely, enlarged the use range of vibrin.Three, the modified polyester resin making Mg-C brick of producing with this method, not only consumption is few, and improve magnesia carbon brick quality (than modified phenolic resins reduced usage quantity 1/5).
A specific embodiment of the present invention is: will cobalt manganese residue be housed respectively with steam, the basin of polyester residue carries out preheating, its preheating temperature be 50-60 ℃ then by pump with two kinds of residues each 60 kilograms, be transported in the reactor that has stirrer and fractional column, and add 2.8 kilograms of glycerol, 0.1 kilogram of yellow lead oxide.With the reactor sealing, stir by the rotating speed of stirrer by 70 rev/mins after feeding intake, simultaneously slow heat temperature raising makes it carry out transesterification reaction.It is reflected at normal pressure, and temperature is to carry out under 160-220 ℃ the condition.Have methyl alcohol to distillate in reaction process, when temperature of reaction reached 220 ℃, constant temperature for some time, when methyl alcohol not had distillated, then transesterification reaction finished.Continue heat temperature raising then, make it carry out polycondensation.Control reaction temperature is 200-240 ℃, and its reaction pressure is vacuum tightness 200-760mmHg.In reaction process, there is ethylene glycol to distillate.When reometer tabular value rising 4-6 ampere, when the stirrer revolution begins to descend, be considered as reaction and finish, stop heating, stir, remove vacuum, reacted material is put into square plate, allow its naturally cooling, curing.By pulverizer solid polyester resin is pulverized then.
Solid-state technical phenol with after the steam dissolving, is got in 650 kilograms of input reactors, got 350 kilograms in formaldehyde again, in 31 kilograms of input reactors of hydrochloric acid, and heat, stir, after 60 minutes, start vacuum pump, control vacuum tightness is 600mmHg, and temperature of reaction is 110 ℃.Stop heating after the reaction beginning, keep reaction after 3 hours, promptly work as reaction solution and be transparent, during no bubble, add industrial soda (NaOH) and neutralize, work as PH=7, falling ball viscosity is that 60-80 is during second, remove vacuum and stop to stir, when the question response temperature is reduced to 40 ℃, liquid phenolic resin is put into storage tank.
With 0.4 ton of liquid phenolic resin, 0.6 ton of polyester resin powder, glycol ether drops in the reactor for 0.21 ton successively, and heating, stirring, control reaction temperature are 100 ℃.After reacting for 1 time, promptly become homogeneous phase when reaction mass, falling ball viscosity is 100-120 during second, stops heating, stirs, with the modified polyester resin barrelling of making.
Claims (7)
1, a kind of preparation method of modified polyester resin is characterized in that:
A, cobalt manganese residue, polyester residue, linking agent and catalyzer are dropped in the reactor, and heat, stir, make it to carry out transesterification reaction, polycondensation, carry out normal vacuum fractionation simultaneously, after treating that methyl alcohol and ethylene glycol distillate, stop heating, stir, remove vacuum, emit material, make its cooling, pulverize after the curing.
B, phenol, formaldehyde, catalyzer are dropped in the reactor, and heat, stir, under reduced pressure make it carry out polyreaction, after the reaction beginning, stop heating, keep reaction for some time, question response liquid neutralizes with alkali after being transparent, no bubble, works as PH=7, falling ball viscosity is that 60-80 is during second, stop to stir, remove vacuum, emit material.
C, with the above-mentioned liquid phenolic resin that makes, polyester resin powder and infiltration thinner are put in the reactor successively, and heating, stir, and make it permeate dilution, become homogeneous phase until reaction mass, till falling ball viscosity is 100-120 second.
2, method according to claim 1, the weight batching ratio that it is characterized in that said cobalt manganese residue, polyester residue, linking agent and catalyzer in a is 0.6: 0.4: 0.03: 0.0005, and its linking agent is a polyvalent alcohol, preferably glycerol, catalyzer is a plumbous oxide, preferably the yellow lead oxide.
3, method according to claim 1 is characterized in that said transesterification reaction in a, and its temperature of reaction is 160-220 ℃, said polycondensation, and its temperature of reaction is 220-240 ℃, reaction pressure is vacuum tightness 200-760mmg.
4, method according to claim 1 is characterized in that the weight batching ratio of said phenol, formaldehyde, catalyzer in b is: 0.55～0.7: 0.3～0.4: 0.002～0.003, and its catalyzer is an acids, preferably hydrochloric acid.
5, method according to claim 1 is characterized in that said polyreaction in b, and its temperature of reaction is 110 ℃ ± 10 ℃, and reaction pressure is vacuum tightness 500～650mmHg.
6, method according to claim 1, the weight batching ratio that it is characterized in that said liquid phenolic resin, polyester resin powder and infiltration thinner in c is: 0.2～0.3: 0.6～0.7: 0.2～0.3, its infiltration thinner is an alcohols, preferably glycol ether.
7, method according to claim 1 is characterized in that said infiltration dilution is to carry out in c under 100 ℃ ± 5 ℃ condition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105103 CN1032347A (en) | 1988-07-28 | 1988-07-28 | The preparation method of modified polyester resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105103 CN1032347A (en) | 1988-07-28 | 1988-07-28 | The preparation method of modified polyester resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1032347A true CN1032347A (en) | 1989-04-12 |
Family
ID=4833333
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88105103 Pending CN1032347A (en) | 1988-07-28 | 1988-07-28 | The preparation method of modified polyester resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1032347A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112521591A (en) * | 2020-11-20 | 2021-03-19 | 黄山市徽州康佳化工有限责任公司 | Polyester resin with lasting high temperature resistance and excellent hardness for powder coating and preparation method thereof |
| CN113696573A (en) * | 2021-10-08 | 2021-11-26 | 宁波勤邦新材料科技有限公司 | Toughened home decoration base film and preparation method thereof |
-
1988
- 1988-07-28 CN CN 88105103 patent/CN1032347A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112521591A (en) * | 2020-11-20 | 2021-03-19 | 黄山市徽州康佳化工有限责任公司 | Polyester resin with lasting high temperature resistance and excellent hardness for powder coating and preparation method thereof |
| CN112521591B (en) * | 2020-11-20 | 2023-04-14 | 黄山市徽州康佳化工有限责任公司 | Polyester resin with lasting high temperature resistance and excellent hardness for powder coating and preparation method thereof |
| CN113696573A (en) * | 2021-10-08 | 2021-11-26 | 宁波勤邦新材料科技有限公司 | Toughened home decoration base film and preparation method thereof |
| CN113696573B (en) * | 2021-10-08 | 2023-07-28 | 宁波勤邦新材料科技有限公司 | Toughened home decoration base film and preparation method thereof |
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| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |