CN102432769A - Unsaturated polyester resin and production method thereof - Google Patents
Unsaturated polyester resin and production method thereof Download PDFInfo
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- CN102432769A CN102432769A CN2011102094175A CN201110209417A CN102432769A CN 102432769 A CN102432769 A CN 102432769A CN 2011102094175 A CN2011102094175 A CN 2011102094175A CN 201110209417 A CN201110209417 A CN 201110209417A CN 102432769 A CN102432769 A CN 102432769A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses unsaturated polyester resin and a production method thereof. The unsaturated polyester resin comprises raw materials of, by weight: 10000-15000 parts of unsaturated polyester resin waste water heavy distillate, 3300-4000 parts of a reaction agent A, 4000-4500 parts of a reaction agent B, 350-450 parts of a reaction agent C, 0.5-0.9 parts of a polymerization inhibitor, 10-15 parts of paraffin, 7000-8500 parts of an active diluent, and 0.4-0.8 parts of a stabilizing agent. The method provided by the invention comprises steps that: a heavy component is obtained from waste water; the heavy component is subject to an alkyd condensation polymerization reaction with the reaction agents; a product is diluted, and a finished product is obtained. With the method, high-concentration waste water can be utilized, such that waste water processing pressure can be greatly reduced, and good environment-protection benefit can be provided. The recovered high-concentration waste water is adopted as a raw material for producing unsaturated polyester resin, such that good economic benefit is provided.
Description
Technical field
The present invention relates to a kind of working method of unsaturated polyester resin, relate to a kind of waste water rectifying particularly and reclaim the method that unsaturated polyester resin is produced in heavy constituent.
Background technology
Unsaturated polyester resin is the most frequently used a kind of in the thermosetting resin, generally is the chain macromolecule compound with ester bond and unsaturated double-bond that is formed by unsaturated dibasic acid divalent alcohol or the unsaturated divalent alcohol polycondensation of monounsaturated dicarboxylic acid.Usually, the polyesterification polycondensation is to carry out at 190～220 ℃, until the acid number that reaches expection (or viscosity); After the reaction end is contracted in polyesterification; Add a certain amount of vinyl monomer while hot, be made into heavy-gravity liquid, such polymers soln is referred to as unsaturated polyester resin.
Structure according to unsaturated polyester resin can be divided into adjacent benzene type, metaphenylene, p-phenyl, bisphenol A-type, vinyl ester type etc.; Can be divided into universal, anti-corrosive type, self-extinguishing type, heat resistant type, low shrinkage type etc. according to its performance; According to its main application can be divided into glass reinforced plastic (FRP) with resin and non-glass steel with two big types of resins.
In the production process of unsaturated polyester resin, contain materials such as unreacted raw material in its waste water, in the prior art, waste water generally burns through the biochemical treatment qualified discharge or after concentrating.These two kinds of means all have its weak point, and the one, caused the wasting of resources, the 2nd, environment there is certain pollution.
Summary of the invention
The object of the present invention is to provide a kind of waste water rectifying to reclaim the method that unsaturated polyester resin is produced in heavy constituent, to solve the problems referred to above that exist in the prior art.
Technical scheme provided by the invention is following:
A kind of unsaturated polyester resin is characterized in that, by weight, this unsaturated polyester resin comprises following raw material:
10000 parts-15000 parts of unsaturated polyester resins wastewater last running;
3300 parts-4000 parts of reagent A;
4000 parts-4500 parts of reagent B;
350 parts-450 parts of reagent C;
Stopper 0.5-0.9 part;
Paraffin 10-15 part;
Reactive thinner 7000-8500 part;
Stablizer 0.4-0.8 part.
Unsaturated polyester resins wastewater double distilled according to the invention is divided into mixture; The staple of the inside is water and saturated di-alcohols (terepthaloyl moietie, Ucar 35, Diethylene Glycol) etc., and wastewater source is in unsaturated polyester resin production processes such as adjacent benzene type, metaphenylene, p-phenyl, bisphenol A-type, vinyl ester types.Waste water passes through rectifying, is concentrated into the about 45%-55% of water ratio.Waste water rectifying and simmer down to prior art can adopt existing rectifying of the industry and concentration technique that saturated di-alcohols is extracted as required.
Aforesaid reagent A is a kind of or its combination in phthalic anhydride, m-phthalic acid, terephthalic acid, THPA, the hexanodioic acid.
Aforesaid reagent B is a kind of or its combination in fumaric acid, cis-butenedioic anhydride, propylenedicarboxylic acid, the cis-methyl-butene diacid.
Aforesaid reagent C is a kind of or its combination in LAURIC ACID 99 MIN, phenylformic acid, sylvic acid, the diacetyl oxide.
Aforementioned stopper is a toluhydroquinone.
Aforementioned reactive thinner is a kind of or its combination in vinylbenzene, alpha-methyl styrene, TEB 3K, Vinyl toluene, the Phthalic acid, diallyl ester.
Aforesaid stablizer is copper naphthenate (YBZJ-02).
A kind of working method of unsaturated polyester resin comprises the steps:
(1) waste water carries out rectifying and concentrates, and obtains last running;
(2) in reaction kettle, drop into waste water last running and reagent A and stir 16-20 ℃ of/hour intensification; When material was warming up to 100 ℃, to slow down heat-up rate be 10-15 ℃/hour and continue temperature reaction; When being warming up to 200-220 ℃, be incubated 0.5-1.5 hour;
(3) reaction mass is cooled to below 155 ℃, in reaction kettle, drop into reagent B and reagent C, 16-20 ℃ of/hour temperature reaction successively; After the reaction water outlet, continue 10-13 ℃/hour of temperature reaction; Control is sticking ℃ in when being warming up to 200 ℃, surveying, and like sticking ℃＜0.20PaS of middle control, continues reaction, until sticking ℃ >=0.20PaS of middle control, can vacuumize the decompression reaction;
In reaction kettle, drop into paraffin, stopper when (4) reaction mass cools to 175-185 ℃ and mix; When being cooled to 160 ℃, opening reaction kettle dilution tunnel valve and dilute.
Preferably, the described heavy constituent water ratio of step (1) is 45-55%
Preferably, before the material dilution, should squeeze into thinner and stablizer in advance in the dilution still, and stir; During dilution, resin remains on 70-90 ℃ in the dilution still.
The present invention is at first with waste water rectifying and concentrated; Obtain containing the composition of saturated di-alcohols (terepthaloyl moietie, Ucar 35, Diethylene Glycol); Utilize the saturated di-alcohols alkyd polycondensation in reagent A and the waste water again; Generate the less macromole polyester of molecular weight, and then utilize reagent B and reagent C that the less macromole polyester of molecular weight is carried out alkyd polycondensation again, obtain the vibrin of macromolecule.
Through method of the present invention, can the waste water reclamation utilization of high density have been alleviated wastewater treatment pressure greatly, can produce good environmental benefit; The high-concentration waste water that reclaims as the raw material production unsaturated polyester resin, can be produced good economic benefit.
The present invention is applicable to the wastewater treatment of the various unsaturated polyester resins that contain water and saturated di-alcohols (terepthaloyl moietie, Ucar 35, Diethylene Glycol) in the waste water.
Embodiment
Embodiment one 191H resin wastewater is produced unsaturated polyester resin
Waste water rectifying concentrates
Below be the spissated embodiment of waste water, but the present invention also can adopt other method rectifying of the industry to concentrate the waste water last running that obtains moisture and saturated di-alcohols components such as (terepthaloyl moietie, Ucar 35, Diethylene Glycols).
1, opens waste water storage tank bottom valve, start the wastewater feed pump, slowly open the wastewater feed variable valve, dominant discharge.(adjusting the flow size as the case may be).
2. when the reboiler liquid level reaches the 200cm left and right sides, slowly open the reboiler heating system, the liquid level that should note observing reboiler this moment, the liquid level of reboiler are controlled at 210cm above (being preferably between the 230cm---260cm).
The liquid level control of reboiler is mainly adjusted through following method: heat the size that gate valve is opened, but maximum control is about 5 teeth 1..2. the produced quantity of heavy constituent size (excessive liquid level is on the low side, and too small liquid level is higher).3. temperature is on the low side, when liquid level is higher, reduces the wastewater feed amount; Temperature rises, and when liquid level is on the low side, increases the wastewater feed amount.
3. when the liquid level of dividing flow container reaches 30cm, open reverse flow valve, start the light constituent reflux pump, carry out total reflux, the quantity of reflux size is according to tower top temperature control (the temperature drift flow strengthens, and temperature is on the low side, and flow reduces).When a minute flow container liquid level reaches 50cm, the beginning extraction, produced quantity divides the height of the liquid level of flow container to decide according to reality, divides the liquid level of flow container to be controlled between the 30---60cm.
4. after the reboiler heating, when the liquid level of reboiler reaches 230cm, open the heavy constituent reflux pump, reflux.
5. the heavy constituent extraction time decides according to the COD of heavy constituent, when COD begins extraction in 100 ± 100,000 scopes.
6. after system's operation is normal, progressively adjust the wastewater feed flow according to the heated oil temperature.
7. control of process parameters:
Wastewater feed amount: 300---1000kg/h, light constituent jar liquid level: 30---50cm
Light constituent output: (adjustment as the case may be). clear water output: (need not control, outlet valve is all opened)
Rectifying column bottom temperature: 95---100 ℃ (deciding) rectifying tower tower top temperature: 90---95 ℃ according to oil temperature practical situation
Rectifying tower bottom pressure: 151kpa (0.15/Mpa). rectifying tower tower top pressure: 131kpa (0.13Mpa).
By above method waste water is carried out rectifying and concentrate, obtain last running, and make this last running water cut about 50%.
In reaction kettle, drop into waste water last running 11500kg, phthalic anhydride 3680kg also stirs, 17 ℃ of/hour intensifications.0.5 hour crawl whisking appliance.
When material is warming up to 100 ℃, slow down heat-up rate, note control head temperature≤105 ℃, and continue temperature reaction (heat-up rate is 13 ℃/hour).When being warming up to 210 ℃, be incubated 1 hour.
Reaction mass is cooled to below 155 ℃, in reaction kettle, drop into fumaric acid 4140kg and LAURIC ACID 99 MIN 391kg, YBZJ-02200g, 17 ℃ of/hour temperature reactions successively.After the reaction water outlet, vertical (type) condenser still head temperature ℃ should control≤and 105 ℃, and continuation temperature reaction (12 ℃/hour).Control viscosity in when being warming up to 200 ℃, surveying,, continue reaction,, can vacuumize the decompression reaction, 1 hour 40 minutes pumpdown time until middle control viscosity >=0.20PaS like middle control viscosity＜0.20PaS.Arrived about 0.095Mpa its half a hour.
Reaction mass cools.In reaction kettle, drop into paraffin 13800g, YBZJ-02490g during to 180 ℃ and mix.When being cooled to 160 ℃, opening reaction kettle dilution tunnel valve and dilute.After material had been put, reaction kettle can be proceeded the next batch production of resins.
Before the material dilution, should squeeze into vinylbenzene 7820kg and copper naphthenate 460ml in advance in the dilution still, and stir.
During dilution, the resin temperature ℃ should remain on 70-90 ℃ in the dilution still.After dilution finished, resin mixed 1hr in this temperature ℃ scope.
When cooling resin to 50-60 ℃, sampling detects resin voltinism index, and according to the voltinism index of test resin is adjusted, until satisfying performance requriements.Notice that the gelation time that will prolong this resin should be used YBZJ-02.
Resin filters through filter, carries out the bucket packing behind the removing solid impurity.
This embodiment 191H resin voltinism index
Outward appearance: the transparent thick liquid of tawny, do not have mechanical impurity;
Viscosity, 25 ℃, Pa.s:0.30---0.35;
Gelation time, 25 ℃, min:6.5---7.5;
The curing system of 191H resin gelling time detecting is: 1.8% promotor YB+1.8% methylethyl ketone peroxide.
Embodiment two 191H resin wastewaters are produced unsaturated polyester resin
The same with embodiment one, at first waste water is carried out rectifying, obtain last running, this last running water cut is 45%.
In reaction kettle, drop into waste water last running 10000kg, terephthalic acid 3300kg also stirs, 19 ℃ of/hour intensifications.0.5 hour crawl whisking appliance.
When material is warming up to 100 ℃, slow down heat-up rate, note control head temperature≤105 ℃, and continue temperature reaction (heat-up rate is 10 ℃/hour).When being warming up to 210 ℃, be incubated 1 hour.
Reaction mass is cooled to below 155 ℃, in reaction kettle, drop into cis-butenedioic anhydride 3550kg and sylvic acid 586kg, YBZJ-02200g, 17 ℃ of/hour temperature reactions successively.After the reaction water outlet, vertical (type) condenser still head temperature ℃ should control≤and 105 ℃, and continuation temperature reaction (12 ℃/hour).Control viscosity in when being warming up to 200 ℃, surveying,, continue reaction,, can vacuumize the decompression reaction, 1 hour 40 minutes pumpdown time until middle control viscosity >=0.20PaS like middle control viscosity＜0.20PaS.Arrived about 0.095Mpa its half a hour.
Reaction mass cools.In reaction kettle, drop into paraffin 13800g, YBZJ-02490g during to 180 ℃ and mix.When being cooled to 160 ℃, opening reaction kettle dilution tunnel valve and dilute.After material had been put, reaction kettle can be proceeded the next batch production of resins.
Before the material dilution, squeeze into vinylbenzene 8000kg and copper naphthenate 460ml in advance in the dilution still, and stir.
During dilution, the resin temperature ℃ should remain on 70-90 ℃ in the dilution still.After dilution finished, resin mixed 1hr in this temperature ℃ scope.
When cooling resin to 50-60 ℃, sampling detects resin voltinism index, and according to the voltinism index of test resin is adjusted, until satisfying performance requriements.Notice that the gelation time that will prolong this resin should be used YBZJ-02.
Resin filters through filter, carries out the bucket packing behind the removing solid impurity.
This embodiment 191H resin voltinism index
Outward appearance: the transparent thick liquid of tawny, do not have mechanical impurity;
Viscosity, 25 ℃, Pa.s:0.30---0.35;
Gelation time, 25 ℃, min:6.5---7.5;
The curing system of 191H resin gelling time detecting is: 1.8% promotor YB+1.8% methylethyl ketone peroxide.
Embodiment three 196H resin wastewaters are produced unsaturated polyester resin
The 196H resin mainly is polymerized by Ucar 35, phthalic anhydride, cis-butenedioic anhydride etc., main moisture and saturated di-alcohols (terepthaloyl moietie, Ucar 35, Diethylene Glycol) etc. in its waste water.
At first waste water is carried out rectifying and concentrate, this last running water cut is about 50%.
All the other embodiments of present embodiment are identical with embodiment one.
Above-mentionedly be merely specific embodiment of the present invention, but design concept of the present invention is not limited thereto, allly utilizes this design that the present invention is carried out the change of unsubstantiality, all should belong to the behavior of invading protection domain of the present invention.
Claims (10)
1. a unsaturated polyester resin is characterized in that, by weight, this unsaturated polyester resin comprises following raw material:
10000 parts-15000 parts of unsaturated polyester resins wastewater last running;
3300 parts-4000 parts of reagent A;
4000 parts-4500 parts of reagent B;
350 parts-450 parts of reagent C;
Stopper 0.5-0.9 part;
Paraffin 10-15 part;
Reactive thinner 7000-8500 part;
Stablizer 0.4-0.8 part.
2. a kind of unsaturated polyester resin as claimed in claim 1 is characterized in that: described reagent A is a kind of or its combination in phthalic anhydride, m-phthalic acid, terephthalic acid, THPA, the hexanodioic acid.
3. a kind of unsaturated polyester resin as claimed in claim 1 is characterized in that: described reagent B is a kind of or its combination in fumaric acid, cis-butenedioic anhydride, propylenedicarboxylic acid, the cis-methyl-butene diacid.
4. a kind of unsaturated polyester resin as claimed in claim 1 is characterized in that: described reagent C is a kind of or its combination in LAURIC ACID 99 MIN, phenylformic acid, sylvic acid, the diacetyl oxide.
5. a kind of unsaturated polyester resin as claimed in claim 1 is characterized in that: said stopper is a toluhydroquinone.
6. a kind of unsaturated polyester resin as claimed in claim 1 is characterized in that: said reactive thinner is a kind of or its combination in vinylbenzene, alpha-methyl styrene, TEB 3K, Vinyl toluene, the Phthalic acid, diallyl ester.
7. a kind of unsaturated polyester resin as claimed in claim 1 is characterized in that: described stablizer is a copper naphthenate.
8. the working method of a unsaturated polyester resin comprises the steps:
(1) waste water carries out rectifying and concentrates, and obtains last running;
(2) in reaction kettle, drop into waste water last running and reagent A and stir 16-20 ℃ of/hour intensification; When material was warming up to 100 ℃, to slow down heat-up rate be 10-15 ℃/hour and continue temperature reaction; When being warming up to 200-220 ℃, be incubated 0.5-1.5 hour;
(3) reaction mass is cooled to below 155 ℃, in reaction kettle, drop into reagent B and reagent C, 16-20 ℃ of/hour temperature reaction successively; After the reaction water outlet, continue 10-13 ℃/hour of temperature reaction; Control is sticking ℃ in when being warming up to 200 ℃, surveying, and like sticking ℃＜0.20PaS of middle control, continues reaction, until sticking ℃ >=0.20PaS of middle control, can vacuumize the decompression reaction;
In reaction kettle, drop into paraffin, stopper when (4) reaction mass cools to 175-185 ℃ and mix; When being cooled to 160 ℃, opening reaction kettle dilution tunnel valve and dilute.
9. the working method of a kind of unsaturated polyester resin as claimed in claim 8, it is characterized in that: it is 45-55% that the described rectifying of step (1) is concentrated into water ratio.
10. the working method of a kind of unsaturated polyester resin as claimed in claim 8 is characterized in that: before the material dilution, should squeeze into thinner and stablizer in advance in the dilution still, and stir; During dilution, resin remains on 70-90 ℃ in the dilution still.
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| CN2011102094175A CN102432769B (en) | 2011-07-25 | 2011-07-25 | Unsaturated polyester resin and production method thereof |
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| CN2011102094175A CN102432769B (en) | 2011-07-25 | 2011-07-25 | Unsaturated polyester resin and production method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105753611A (en) * | 2016-01-11 | 2016-07-13 | 湖北省农业科学院植保土肥研究所 | Unsaturated polyester coated controlled-release fertilizer prepared from PET wastes and preparation method thereof |
| CN106589749A (en) * | 2016-12-03 | 2017-04-26 | 安徽富丽华化工有限公司 | Modified unsaturated polyester resin having excellent acid and alkali resistance, and preparation method thereof |
| CN107362567A (en) * | 2017-08-29 | 2017-11-21 | 湖北工程学院 | A kind of distillation system and solvent purification system |
| CN109232870A (en) * | 2018-09-11 | 2019-01-18 | 惠州市固德尔合成材料有限公司 | A kind of recycling and reusing method of unsaturated-resin synthesis process waste liquid |
| CN116375948A (en) * | 2023-02-23 | 2023-07-04 | 鑫双利(惠州)树脂有限公司 | Polar molecule modified unsaturated polyester resin and preparation method thereof |
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| CN1508167A (en) * | 2002-12-19 | 2004-06-30 | 陈少岳 | Method for producing unsaturated polyester resin by utilizing refuse of biatomic acid such as terephthalic acid and catalyst used thereof |
| CN1844187A (en) * | 2006-03-23 | 2006-10-11 | 华东理工大学华昌聚合物有限公司 | Process for producing terephthalic unsaturated polyester resin by using terephthalic acid rinsing residue |
| CN101353418A (en) * | 2007-07-24 | 2009-01-28 | 中山联成化学工业有限公司 | Method for preparing unsaturated polyester resin from wastes of benzoic anhydride production process and distillation fraction |
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2011
- 2011-07-25 CN CN2011102094175A patent/CN102432769B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1508167A (en) * | 2002-12-19 | 2004-06-30 | 陈少岳 | Method for producing unsaturated polyester resin by utilizing refuse of biatomic acid such as terephthalic acid and catalyst used thereof |
| CN1844187A (en) * | 2006-03-23 | 2006-10-11 | 华东理工大学华昌聚合物有限公司 | Process for producing terephthalic unsaturated polyester resin by using terephthalic acid rinsing residue |
| CN101353418A (en) * | 2007-07-24 | 2009-01-28 | 中山联成化学工业有限公司 | Method for preparing unsaturated polyester resin from wastes of benzoic anhydride production process and distillation fraction |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105753611A (en) * | 2016-01-11 | 2016-07-13 | 湖北省农业科学院植保土肥研究所 | Unsaturated polyester coated controlled-release fertilizer prepared from PET wastes and preparation method thereof |
| CN106589749A (en) * | 2016-12-03 | 2017-04-26 | 安徽富丽华化工有限公司 | Modified unsaturated polyester resin having excellent acid and alkali resistance, and preparation method thereof |
| CN107362567A (en) * | 2017-08-29 | 2017-11-21 | 湖北工程学院 | A kind of distillation system and solvent purification system |
| CN109232870A (en) * | 2018-09-11 | 2019-01-18 | 惠州市固德尔合成材料有限公司 | A kind of recycling and reusing method of unsaturated-resin synthesis process waste liquid |
| CN116375948A (en) * | 2023-02-23 | 2023-07-04 | 鑫双利(惠州)树脂有限公司 | Polar molecule modified unsaturated polyester resin and preparation method thereof |
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| CN102432769B (en) | 2013-02-27 |
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