CN108424511A - A kind of method and application using printing and dyeing screenings manufacture aqueous polyester resin - Google Patents
A kind of method and application using printing and dyeing screenings manufacture aqueous polyester resin Download PDFInfo
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- CN108424511A CN108424511A CN201810272327.2A CN201810272327A CN108424511A CN 108424511 A CN108424511 A CN 108424511A CN 201810272327 A CN201810272327 A CN 201810272327A CN 108424511 A CN108424511 A CN 108424511A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/127—Acids containing aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a kind of method and applications manufacturing aqueous polyester resin using printing and dyeing screenings.The terephthalic acid (TPA) mixed organic acid that acid out goes out from printing and dyeing alkali decrement waste water or boil off waste water of printing and dyeing produces aqueous polyester resin, for fields such as material in polyester resin, aqueous polyester resin coating, aqueous polyester resin adhesives, the present invention has innovated superfine aqueous polyester resin manufacture method.Resources circulation turns waste into wealth.Using this principle and condition, the multipurpose application approach of terephthalic acid (TPA) mixed organic acid can be opened.Complete aqueous polyester resin is manufactured, the manufacturing technical feature of the aqueous polyester resin of conventionally employed alkali neutralization acid carboxyl is also improved, does not have solvent VOC, generates complete environmental-friendly aqueous polyester resin product, Social benefit and economic benefit is huge.
Description
Technical field
The invention belongs to textile printing and dyeing wastewater process fields, and in particular to a kind of to manufacture waterborne polyester tree using printing and dyeing screenings
The method of fat and application.
Background technology
We have a large amount of textile printing and dyeing enterprises in national some areas, there is the production of dyeing and finishing Alkali reduction and dyeing and finishing boil off in enterprise
Technique processing line, the terylene and chemical fibre cotton cloth of daily thousands of tons, by decrement and boil off, enter from dyeing and finishing processing line
Road dyeing process afterwards.In the machining process of Alkali reduction and boil off, there is a large amount of decrement object terephthalic acid (TPA) (PTA) and mix
It closes organic acid acid out to come out, i.e., white screenings (white clay).But the organic matter infusibility indissoluble, synthesis temperature is high, and product fisheye is high, viscous
Degree is big, is restricted using process applications.National dyeing dyeing and finishing wastewater Alkali reduction by-product and boil off slag waste are every year extremely
It is few there are about the discharge capacity of ten thousand tons of 10-30, be a very huge quantity.Because the PTA of recycling does not apply outlet well, entirely
Portion enters drainage, and COD is made to increase significantly, and pollutes local environment system.
Terephthalic acid (TPA) is mainly used for production dacron polyester, secondly synthesizing polyester resin, high-grade paint, high-grade gluing
Agent, plasticizer, other advanced-engineered materials etc..Dyeing waste water acid out terephthalic acid (TPA) mixed organic acid, purity is not high, less than washing
Synthetic fibre grade, and brought printing and dyeing colorant into, can not produce opaque products, re-refine extremely difficult, constrain the bottleneck recycled.By
Terephthalic acid (TPA) mixed acid and dibasic alcohol ester polymeric polyester production of chemicals mixing saturated polyester resin, by linear condensation and
Cross-linked network generates mixed polyester high molecular material, is modified by technology, becomes the industry for dissolving saturated polyester and unsaturated polyester (UP)
Product is produced, is a kind of technical method of innovation.
According to innovative material technical characterstic, aqueous saturated polyester resin material, aqueous polyester resin adhesive, aqueous is developed
The products such as Polyester resin lacquer are a kind of directions of complete innovation and development.Aqueous saturated polyester resin production technology, at home state
Also there is certain advance, domestic technology and grade quality to have a certain distance with world standard outside, we by using
Dyeing waste water recycles waste material and produces aqueous polyester resin material, innovation transformation traditional processing technology route, and difference uses alkali neutralization
The method of organic acid carboxyl, completely dispenses with organic solvent diluting, a kind of completely new aqueous saturated polyester resin product of innovation,
The pollution of VOC ingredients is not generated in technique and product, has produced green product, has reached environmentally protective production and what is used wants
It asks.
Invention content
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of utilization printing and dyeing screenings manufacture waterborne polyester tree
The method and its application of fat.
A method of aqueous polyester resin being manufactured using printing and dyeing screenings, its step are as follows：
1) acid out extracts the wet organic acid solid containing terephthalic acid (TPA) from printing and dyeing alkali decrement waste water, printing and dyeing boil off waste water；
2) directly slurrying is mixed with dihydric alcohol or polyalcohol in the wet organic acid solid that step 1) obtains, and is added after slurrying
Lactate synthesis reactor, wherein the molar ratio of the hydroxyl in the carboxyl and alcohol of wet organic acid solid is 1: 2-3；
3) it under atmosphere of inert gases, is first dehydrated；Organic acid and alcohol carries out esterification again；
4) reaction kettle lactate synthesis waste heat is utilized, devolatilization, the extra alcohol of removing unreacted are vacuumized, vacuum degree is maintained at
0.01Mpa-0.05Mpa, time are 10-30 minutes；Then will esterification generate hydroxyl telechelic polyester product be cooled to 140 DEG C with
Under, obtain aqueous polyester resin.
Preferably, the step 1) is specially：
Insoluble mechanical admixture is removed by filtration in printing and dyeing alkali decrement waste water, printing and dyeing boil off waste water, and acid out is mixed in acid adding,
The pH value for controlling acid out waste water is 2-5；Organic acid solid is centrifuged out, then is washed with clear water until the pH value of washings is 6-
7, it is centrifuged repeatedly dehydration later, obtains the organic acid solid that aqueous mass percent is 40-70%.
Preferably, the acid that the acid out adds is the sulfuric acid of " 98% ".
Preferably, the molar ratio of the hydroxyl in the carboxyl and alcohol of mixed acid is preferably 1: 2.1-2.5.
Preferably, the dihydric alcohol be ethylene glycol, propylene glycol, neopentyl glycol, butanediol and polyalcohol in one kind or
It is a variety of.
Preferably, the step 3) is specially：Lactate synthesis reactor is replaced with nitrogen；Control heating rate is 2-4
DEG C/min, react 30-60min；Tower top constantly steams moisture at this time, after water outlet to be distilled 1-2 hours, closes reactor cooling system
System connects open to atmosphere outlet valve, and reactor is made to heat up with 30-50 DEG C/h speed, after temperature reaches 170-190 DEG C in kettle, after of continuing rising
The moisture that esterification generates is discharged with reaction in temperature reaction 2-3 hours；It is further continued for heating up with 10-30 DEG C/h speed, at 220-260 DEG C
Under the conditions of react, to occur tower top temperature automatically decline and no liquid steam when or tower top temperature drop to 150 DEG C or less when, stopping
Reaction.The above-mentioned preferred synthetic method of the present invention, esterification of the end reaction temperature than traditional terephthalic acid (TPA) and dihydric alcohol
Reaction temperature is 30-40 DEG C low, can reduce energy consumption of reaction, avoids resin polymerization degree excessively high, influences subsequently on probation.
Further, the step 3) is specially：Before temperature reaction, air in kettle is extracted out, purged three times, pressed with nitrogen
The speed heating of 2-4 DEG C of heating per minute, reacts 40-45min, reaction kettle tower top temperature can reach 100 DEG C or more at this time, tower
Top constantly steams the moisture added, and after distillation is discharged 1-2 hours, kettle temperature slightly rises, and closes the connection of reactor cooling system
The outlet valve of air；Make reactor continue to heat up with 30-50 DEG C/h of speed, so that temperature in kettle is reached 170-190 DEG C, slowly
Temperature reaction 2-3 hours controls tower top temperature with overhead reflux, and reactor pressure is in 0.03-0.5Mpa, in time discharge esterification
The moisture of generation is further continued for using 10-30 DEG C/h of heating rate, is reacted under the conditions of making kettle temperature be 220 DEG C to 260 DEG C, to appearance
When tower top temperature declines automatically, no liquid steams, or top temperature drops to 150 DEG C or less and stops reaction.
The invention also discloses the application for the aqueous polyester resin that the method is prepared, the aqueous polyester resin is used
In preparing aqueous saturated polyester resin material, aqueous polyester resin adhesive or aqueous polyester resin coating.
The invention also discloses a kind of aqueous polyester resin being prepared in this way paste resins as main component
Material, preparation method are as follows：
1) aqueous polyester resin is matched into clear water, wherein the mass ratio of aqueous Ju esters Shu Zhi ︰ water is 3 ︰ 4-6, by sending
Material, which is pumped into super grinder, is milled to translucent slurry, saves as the basic main material of estrodur performed polymer；
2) curing agent is added in the basic main material of estrodur performed polymer, the curing agent is resol resins, aqueous ammonia
Base resin, aqueous epoxy resins, waterborne polyurethane resin, aqueous acetal resin, water-based acrylic resin, aqueous fluorine-containing silicones
In it is one or more, the mass ratio of the basic Zhu Cai ︰ curing agent of performed polymer is 5 ︰ 1-5；Polyester resin function additive, polyester is added
Resin function additive addition is 1-10wt%, adjusts the pH value of resin slurry within the scope of 7-9.
The invention also discloses a kind of application processes of the resin slurry, and resin slurry is coated, impregnate, is mixed into
To being applied on leaching inner or surface, first low temperature is slowly dehydrated before baking-curing, and dehydration temperaturre is less than 60 DEG C, avoids generating gas
Bubble makes coating gluing object be brought rapidly up 120-200 DEG C, baking time is 5-60 minutes, is reached when moisture removal is clean
Heat cure cross-linked network.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) terephthalic acid (TPA) of printing and dyeing alkali decrement waste water acid out, the organic acid mixture for boil off waste water acid out of printing and dyeing are utilized
With other polyacids, and dihydric alcohol or other polyalcohol chemical synthesis mixed polyesters, then crushes or be directly diluted with water and be finely ground to
Translucent pulpous state is manufactured into aqueous hybrid polyester resin, is a kind of completely new resource circulation utilization manufacture waterborne polyester innovation hair
It is bright.
(2) terephthalic acid (TPA) mol ratio dosage increases in the complete aqueous polyester resin of new process production, crystalline temperature
Height, intensity improve, and heat-resist, application surface is extensive, complete solvent-free VOC, aqueous, environmental protective, green product.
(3) new aqueous polyester resin low price terephthalic acid (TPA) dosage is more, at low cost, good in economic efficiency, printing and dyeing acid out slurry
Slag resource circulation utilization, turns waste into wealth, and economic results in society are notable.
To sum up described in 3 points, printing and dyeing alkali decrement waste water acid out terephthalic acid (TPA), printing and dyeing boil off waste water acid out organic acid are utilized
Mixture and other polyacids, with dihydric alcohol or other polyalcohol chemical synthesis organic acid mixed polyesters, thus it is possible to vary aqueous painting
In material and Aqueous Adhesives industry, the sky of technology and kind in the method for manufacture and use thereof for aqueous polyester resin has been filled up
In vain, performance condition can reach and exceed the level of solvent type polyester product, be worth promoting and advocate use.
Specific implementation mode
The object of the present invention is to provide a kind of methods manufacturing aqueous polyester resin using printing and dyeing screenings.
With the organic acids such as the terephthalic acid (TPA) that acid out extracts from printing and dyeing alkali decrement waste water and boil off waste water of printing and dyeing, then and storage
Dihydric alcohol or polyalcohol in slot and polyacid are stirred slurrying, by reaction in ratio addition alkyd mixing vessel as required
It is required that the ratio that proportioning organic acid and dihydric alcohol are 1: 2-3mol is stirred, optimal proportion 1: 2.1-2.5mol；Dihydric alcohol
Can be ethylene glycol, propylene glycol, neopentyl glycol, butanediol and polyalcohol etc..The dihydric alcohol amount of skipping over, lactate synthesis will more fully.
Further to adjust polyester resin performance, other binary acid can also be added, binary acid can use adipic acid, certain herbaceous plants with big flowers
Diacid or most common aromatic acid phthalic acid, M-phthalic acid, terephthalic acid (TPA), phthalic anhydride, ternary acid etc. are by wanting
Ask ratio compounding synthesis, the ratio of general terephthalic acid (TPA) that can account for 30%-70% or more, other binary acid account for 20%-
50%.The kind that polyacid and polyalcohol synthesizing polyester resin is added can be more diversified, and performance can be more comprehensively.
Mixed organic acid in alkyd mixer and diol mixture are worn into screened stock with colloid, lactate synthesis is added
In reactor, esterifier is accompanied with agitating paddle, dehydration distillation tower, condenser, reflux meter, product baiting valve, electronics
The subsidiary functional structure devices such as hot plate, condensation polyalcohol storage tank, distillation condensed water storage tank, vacuum system, nitrogen cylinder；It opens
Beginning temperature reaction lactate synthesis.Before temperature reaction, air in kettle is extracted out, purged three times with nitrogen.By 2-4 DEG C of heating per minute
Speed heats, and reacts 40 minutes or so, reaction kettle material temperature in kettle is 130 DEG C or so at this time, and reaction kettle tower top temperature can reach
To 100 DEG C or more, tower top constantly steams the moisture added this moment, and after distillation is discharged 1-2 hours, kettle temperature slightly rises, i.e.,
It closes reactor cooling system and connects open to atmosphere outlet valve.Make reactor continue to heat up with 30-50 DEG C/h of speed, makes kettle
Interior temperature reaches 180 DEG C or so, starts to have pressure in the kettle of 0.01Mpa or so, and esterification slowly starts.Slow temperature reaction
2-3 hours, tower top temperature is controlled with overhead reflux, pressure can be in 0.03-0.5Mpa or so, the water of the generation of discharge esterification in time
Point.It is further continued for using 10-30 DEG C/h of heating rate, be reacted 2-3 hours under the conditions of making kettle temperature be 220 DEG C to 260 DEG C, to appearance
When tower top temperature declines automatically, no liquid steams, and illustrates that esterification terminates.(or top temperature drops to 150 DEG C or less) stops
Reaction.Pressure can be 0.1Mpa or more (up to 0.3-0.5Mpa) at this time.
After esterification, using reaction kettle lactate synthesis waste heat, opens vacuum pump and vacuumize devolatilization, remove unreacted
Extra dihydric alcohol, vacuum degree is not so high, vacuumizes ＜ 30 minutes, controls vacuum degree, prevents esterification products depth polycondensation, keep away
Exempt to generate excessive high poly- product, gelation cannot absolutely occur.Then the hydroxyl telechelic polyester product that esterification generates is cooled to 140
DEG C hereinafter, discharging, be granulated, packaging.Obtain the low molecular weight polyester product of the multi items class of acid value ＜ 10NaOHmg/l.Esterification life
Production. art control uses computer automation intelligent control.
Embodiment 1
1200L stainless steel cauldrons, pilot scale material 900KG (including water), for Alkali reduction boil off slag of printing and dyeing；Wherein to benzene two
Formic acid content is 97% or more；With obtaining wet organic acid solid after 98% sulfuric acid acid out；
Acid out method is：Acid out is mixed in acid adding, and the pH value of control acid out waste water is 2-5；Centrifuge out organic acid
Solid, then washed with clear water until the pH value of washings is 6-7, it is centrifuged repeatedly dehydration later, obtains aqueous mass percent as 40-
70% organic acid solid.
Proportioning You Ji Suan ︰ ethylene glycol molar ratio=and it is 1 ︰ 2.8, esterification is carried out, reaction process is：Before temperature reaction,
It extracts air in kettle out, is purged three times with nitrogen.It is heated by the speed of 2-4 DEG C of heating per minute, reaction 40 minutes or so, at this time instead
It is 130 DEG C or so to answer kettle material temperature in kettle, and reaction kettle tower top temperature can reach 100 DEG C or more, first be dehydrated, and tower top is not this moment
Disconnected to steam the moisture added, after distillation is discharged 1-2 hours, kettle temperature slightly rises, that is, closes the connection of reactor cooling system greatly
The outlet valve of gas.Make reactor continue to heat up with 30-50 DEG C/h of speed, so that temperature in kettle is reached 180 DEG C or so, start meeting
There are pressure in the kettle of 0.01Mpa or so, esterification slowly to start.Slow temperature reaction 2-3 hours, is controlled with overhead reflux
Tower top temperature, pressure can be in 0.03-0.5Mpa or so, the moisture of the generation of discharge esterification in time.It is further continued for using heating rate 10-30
DEG C/h, it is reacted 2-3 hours under the conditions of making kettle temperature be 220 DEG C to 260 DEG C, to when tower top temperature occur and declining automatically, without liquid
Body steams, and illustrates that esterification terminates.(or top temperature drops to 150 DEG C or less) stops reaction.At this time pressure can be 0.1Mpa or
(up to 0.3-0.5Mpa) above.
Control 230-260 DEG C of final temperature, reaction pressure 0.5Mpa, total reaction time 12h；It is organic to obtain the mixing of pilot scale product
Sour glycol ester 300KG, acid value 3KOHmg/L, color and luster ash are milky white.
Above-mentioned powdery mixed organic acid glycol ester 70%+ amino resins 30% is uniformly mixed, or the 70% of the amount of totalling again
Pure water, colloid mill is levigate, and coating, dipping, spraying, compression molding, 140 DEG C are toasted 40 minutes, obtain amino resins be modified it is mixed
Close polyester resin sample.
Embodiment 2
Compared with Example 1, match difference lies in You Ji Suan ︰ ethylene glycol=it is 1 ︰ 2.1mol, reaction temperature 230-260
DEG C, reaction pressure 0.5Mpa, total reaction time 12h；Pilot scale product 300KG, acid value 3KOHmg/L, color and luster ash are milky white.
Above-mentioned powdery mixed organic acid glycol ester 70%+ polyurethane resins 30% be uniformly mixed, then the amount of totalling 70%
Pure water, colloid mill is levigate, coating, dipping, spraying, compression molding, 140 DEG C toast 40 minutes, obtain polyurethane-modified mixing
Polyester resin sample.
Embodiment 3
Compared with Example 1, match difference lies in You Ji Suan ︰ ethylene glycol=it is 1 ︰ 2.5mol, reaction temperature 230-260
DEG C, reaction pressure 0.5Mpa, total reaction time 12h；Pilot scale product 300KG, acid value 3KOHmg/L, color and luster ash are milky white.
Above-mentioned powdery mixed organic acid glycol ester 70%+ phenolic resin 30% is uniformly mixed, then the amount of totalling 70%
Pure water, colloid mill is levigate, and coating, dipping, spraying, compression molding, 140 DEG C are toasted 40 minutes, and phenolic resin modified mixing is obtained
Polyester resin sample.
After tested, the degree of polymerization for the pilot scale product (based on bis-glycol terephthalate) that embodiment 1-3 is obtained is about
It is 2；(resin in water：3 ︰ 4-6 of water ratio) it can long-time stable dispersion.
Terephthaldehyde's acid content is more than 60% in printing and dyeing boil off waste water, and other compositions are mainly acrylic acid mixed organic acid.
Using it as raw material, using the method for embodiment 1,1200L stainless steel cauldrons, raw material 900KG (including water), You Ji Suan ︰ second two
Alcohol matches=and it is 1 ︰ 2.5mol, pilot scale product 280KG, acid value 3KOHmg/L, color and luster ash is milky white.
The product main component that the present invention obtains is the double binary alcohol esters of terephthalic acid (TPA), the product that embodiment obtains mainly at
It is divided into bis-glycol terephthalate, matches a certain proportion of clear water, the quality of the double ethylene glycol Zhi ︰ water of general terephthalic acid (TPA)
Ratio is 3 ︰ 4-6, and fluidity of slurry is good when optimum proportioning, and solid content is high.It is pressed into super grinder by feed pump and is milled to half
The fineness of transparent slurry, solid ester reaches submicron order or nanoscale, and solid ester is dissolved or suspended in waterborne polyester slurry substantially
In product, has best intersolubility, for the purpose of not generating layering when slurry product being made to store for a long time.Storage is used as waterborne polyester tree
The basic main material of estrodur performed polymer of fat, waterborne polyester adhesive, waterborne polyester coating etc..
Make the basic main material of performed polymer as main component with above-mentioned waterborne polyester, by the way that different cultivars and mass ratio is added
Curing agent, stir homogeneous, heat netted crosslinking curing.Curing agent, which is used as, is crosslinked main component, and generally less than 30%.It is available
Optimized solidification agent type has：Resol resins, water-compatible amino resin, aqueous epoxy resins, waterborne polyurethane resin；Also it can be used
Have aqueous acetal resin, water-based acrylic resin, aqueous fluorine-containing silicones etc. with active reaction can be played with hydroxyl or carboxyl
Organic matter.Curing agent resin must be water-soluble or water-based emulsion or water slurry, and basic main material waterborne polyester tree
Fat performed polymer has a good compatibility, and cannot carry and generate the remaining water-miscible organic solvents of VOC and other can degrade
Organic matter auxiliary agent.5 ︰ 1-5 are generally usually using the mass ratio that range is aqueous polyester resin Yu Ju Ti ︰ curing agent, most preferably
5 ︰ 1-2.Preferably proportioning can be 1 ︰ 1- by calculating active functionality's MOL equivalents of aqueous polyester resin Yu Ju Ti ︰ curing agent
1.05。
The polyester resin of different use occasions needs the polyester resin function additive for adding different performance.Polyester resin
Major function auxiliary agent category has：Reinforcing agent, tackifier, emulsifier, levelling agent, bleeding agent, softening agent, pigment, fire retardant etc., most
Good addition is 1%-10%.Other auxiliary agents have water repellent agent, anti-aging agent, weather resisting agent, guarantor's photo etching, filler etc., are chemically synthesized
And allotment, meet compatible Mechanism according to function needs according to reaction principle, adjusts ratio, change polyester resin items work(
Energy.
Aqueous polyester resin finally also needs to the pH value of adjustment resin slurry, it is desirable that pH value controls within the scope of 7-9, most preferably
PH is to keep the partially faint alkalinity of slurry neutrality in 7.0-7.5 ranges, prevent hydrolysis, resin quality can be made to stablize, and extends storage
Deposit the phase.
For the embodiment of the present invention using ethylene glycol as polyalcohol, the typical polyester for reacting synthesis is mainly terephthalic acid (TPA) pair second two
Alcohol ester, the solid that " bis-glycol terephthalate " product mixture fusing point that the present invention synthesizes is≤110 DEG C, certified products is white
Color waxy solid object, fusing point is low, water-soluble.Printing and dyeing screenings recycling produce product grayish, appearance is not multiple
With being also solid-state like before processing, it can subsequently crush that be made be solid, powdery；Water can also be added to compound synthetic reaction tune
Be made the aqueous polyester resin of slurry state, or according to performance need depending on shape.May be used when tooling direct impregnation,
The relative productions construction technologies such as coating, spraying, film modeling hot pressing, baking.
The solidification of the present invention is using baking heat cure using the technique best approach.First resin is coated, impregnate, is mixed into
Enter to being applied on leaching inner or surface, coating wants thin, and workpiece should not be too thick.The first short time is low with conveyer belt before baking-curing
Warm slowly dehydration, dehydration temperaturre do not exceed 60-90 DEG C, avoid generating bubble.When moisture removes clean soon, make coating gluing
Object is brought rapidly up 120-200 DEG C, and best temperature is 120-150 DEG C.Baking time is 5-60 minutes, Best Times 5-
20 minutes, curable polyester resin baking temperature and time were adjusted as needed, reaches heat cure cross-linked network, prevents polyester resin
Solidification was generated when baking, embrittlement is carbonized, and decomposes, influences resin forming quality.
It can also be used for saturated polyester resin crosslinking curing made of main material using printing and dyeing screenings terephthalic acid (TPA)
Daily temperature-curable, such as it is previously added in lactate synthesis reaction process the unsaturated carboxylic acid anhydride with double bond or without double bond alcohol
Sour organic matter raw material grafting synthesis, can be made into unsaturated polyester resin or saturated polyester resin, then product insatiable hunger polyester tree
The compatibility of fat and saturated polyester resin and water wants the more of difference.The process for adding water mill thin, or addition diluent can also be used,
Addition curing catalysts solidification at normal temperatures.Unsaturated polyester resin curing catalysts have：Acid and alkaline matter, ammonia and amine
Substance, peroxide, metallic compound etc..There are commonly：Sulfonic acid, sulfuric acid, NaOH, ammonium hydroxide, organic amine, hydrogen peroxide, peroxidating
Methyl ethyl ketone, cobalt naphthenate etc. select to use according to resin variety, can accomplish to cure crosslinking at normal temperatures.Curing catalysts dosage
Generally 0.1%-10%, most preferably 0.1%-5%.It is fireballing to curing reaction to use the double groups of A resins, B-tree fat
Part, the used time, interim mixture used.
By experimental exploration, it is completed and establishes 500 tons/year of aqueous polyester resin scale up test model equipments, feasibility
Running analysis design scheme.It can finally develop and include at one：Screenings recycling-synthesizing polyester resin-compounding engineering material-
The PTA and screenings PTA mixtures of end product derive the completely new environmentally protective industrial chain of multi items, innovate and fill up domestic and continue
The resource product industrial structure in emerging area has created primary condition for recycling, saves petroleum product resource, change give up into
Treasured creates huge social benefit and economic benefit.
Claims (10)
1. a kind of method using printing and dyeing screenings manufacture aqueous polyester resin, it is characterised in that steps are as follows：
1) from printing and dyeing alkali decrement waste water, printing and dyeing boil off waste water acid out extraction containing the wet organic acid solid based on terephthalic acid (TPA)；
2) directly slurrying is mixed with dihydric alcohol or polyalcohol in the wet organic acid solid that step 1) obtains, and esterification is added after slurrying
Synthesis reactor, wherein the molar ratio of the hydroxyl in the carboxyl and alcohol of wet organic acid solid is 1: 2-3；
3) it under atmosphere of inert gases, is first dehydrated；Organic acid and alcohol carries out esterification again；
4) reaction kettle lactate synthesis waste heat is utilized, devolatilization, the extra alcohol of removing unreacted are vacuumized, vacuum degree is maintained at
0.01Mpa-0.05Mpa, time are 10-30 minutes；Then will esterification generate hydroxyl telechelic polyester product be cooled to 140 DEG C with
Under, obtain aqueous polyester resin.
2. the method according to claim 1 using printing and dyeing screenings manufacture aqueous polyester resin, it is characterised in that described
Step 1) is specially：
Insoluble mechanical admixture is removed by filtration in printing and dyeing alkali decrement waste water, printing and dyeing boil off waste water, and acid out, control is mixed in acid adding
The pH value of acid out waste water is 2-5；It centrifuges out organic acid solid, then is washed with clear water until the pH value of washings is 6-7, it
After be centrifuged repeatedly dehydration, obtain aqueous mass percent be 40-70% organic acid solid.
3. according to 2 methods for manufacturing aqueous polyester resin using printing and dyeing screenings stated are required, it is characterised in that the acid out added
Acid is the sulfuric acid of " 98% ".
4. according to the method for manufacturing aqueous polyester resin using printing and dyeing screenings required described in 1, it is characterised in that the carboxylic of mixed acid
The molar ratio of base and the hydroxyl in alcohol is preferably 1: 2.1-2.5.
5. the method using printing and dyeing screenings manufacture aqueous polyester resin that claim 1 is stated, it is characterised in that the dihydric alcohol
It is one or more in ethylene glycol, propylene glycol, neopentyl glycol, butanediol and polyalcohol.
6. the method using printing and dyeing screenings manufacture aqueous polyester resin that claim 1 is stated, it is characterised in that the step 3)
Specially：
Lactate synthesis reactor is replaced with nitrogen；Control heating rate is 2-4 DEG C/min, reacts 30-60min；Tower top is not at this time
Disconnected to steam moisture, after water outlet to be distilled 1-2 hours, closing reactor cooling system connects open to atmosphere outlet valve, makes reactor
It is heated up with 30-50 DEG C/h speed, after temperature reaches 170-190 DEG C in kettle, continues temperature reaction 2-3 hours, with reaction discharge esterification
The moisture of generation；It is further continued for heating up with 10-30 DEG C/h speed, be reacted under the conditions of 220-260 DEG C, it is automatic to there is tower top temperature
Decline and no liquid is when steaming or when tower top temperature drops to 150 DEG C or less, stops reacting.
7. the method using printing and dyeing screenings manufacture aqueous polyester resin that claim 1 is stated, it is characterised in that the step 3)
Specially：
Before temperature reaction, air in kettle is extracted out, purged three times with nitrogen, heated by the speed of 2-4 DEG C of heating per minute, reaction
40-45min, at this time reaction kettle tower top temperature can reach 100 DEG C or more, tower top constantly steams the moisture added, and distills out
After water 1-2 hours, kettle temperature slightly rises, and closes reactor cooling system and connects open to atmosphere outlet valve；Make reactor continue with
30-50 DEG C/h of speed heating, makes temperature in kettle reach 170-190 DEG C, slow temperature reaction 2-3 hours, is controlled with overhead reflux
Tower top temperature processed, the moisture that reactor pressure is generated in 0.03-0.5Mpa, in time discharge esterification are further continued for using heating rate 10-
It 30 DEG C/h, reacts under the conditions of making kettle temperature be 220 DEG C to 260 DEG C, to when tower top temperature occur and declining automatically, is steamed without liquid
Go out, or top temperature drops to 150 DEG C or less and stops reaction.
8. a kind of application for the aqueous polyester resin that claim 1 the method is prepared, it is characterised in that described aqueous poly-
Ester resin is used to prepare aqueous saturated polyester resin material, aqueous polyester resin adhesive, aqueous polyester resin coating.
9. a kind of aqueous polyester resin being prepared with claim 1 the method resin slurry as main component, special
Sign is that preparation method is as follows：
1) aqueous polyester resin is matched into clear water, wherein the mass ratio of aqueous Ju esters Shu Zhi ︰ water is 3 ︰ 4-6, passes through feeding engine
It is pressed into super grinder and is milled to translucent slurry, save as the basic main material of estrodur performed polymer；
2) curing agent is added in the basic main material of estrodur performed polymer, the curing agent is resol resins, aqueous amino tree
In fat, aqueous epoxy resins, waterborne polyurethane resin, aqueous acetal resin, water-based acrylic resin, aqueous fluorine-containing silicones
One or more, the mass ratio of the basic Zhu Cai ︰ curing agent of performed polymer is 5 ︰ 1-5；Polyester resin function additive, polyester resin is added
Function additive addition is 1-10wt%, adjusts the pH value of resin slurry within the scope of 7-9.
10. the application of resin slurry described in a kind of claim 8, it is characterised in that：Resin slurry is coated, impregnate, is mixed into
Enter to being applied on leaching inner or surface, first low temperature is slowly dehydrated before baking-curing, and dehydration temperaturre is less than 60 DEG C, avoids generating
Bubble makes coating gluing object be brought rapidly up 120-200 DEG C, baking time is 5-60 minutes, is reached when moisture removal is clean
To heat cure cross-linked network.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101503510A (en) * | 2009-03-09 | 2009-08-12 | 嘉兴市清河高力绝缘有限公司 | Preparation of water-soluble polyester resin for silicon steel sheet insulation processing |
| WO2010119317A1 (en) * | 2009-04-14 | 2010-10-21 | Basf Coatings Japan Ltd. | Aqueous mid-coat paint composition |
| CN104231879A (en) * | 2014-09-16 | 2014-12-24 | 北京高盟燕山科技有限公司 | Water-based polyester primer for enhancing printing and aluminum plating and preparation method of water-based polyester primer |
| CN106277576A (en) * | 2016-08-11 | 2017-01-04 | 上海凯鑫分离技术股份有限公司 | A kind of polyester fiber alkali processes the integrated conduct method of waste water |
-
2018
- 2018-03-29 CN CN201810272327.2A patent/CN108424511B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101503510A (en) * | 2009-03-09 | 2009-08-12 | 嘉兴市清河高力绝缘有限公司 | Preparation of water-soluble polyester resin for silicon steel sheet insulation processing |
| WO2010119317A1 (en) * | 2009-04-14 | 2010-10-21 | Basf Coatings Japan Ltd. | Aqueous mid-coat paint composition |
| CN104231879A (en) * | 2014-09-16 | 2014-12-24 | 北京高盟燕山科技有限公司 | Water-based polyester primer for enhancing printing and aluminum plating and preparation method of water-based polyester primer |
| CN106277576A (en) * | 2016-08-11 | 2017-01-04 | 上海凯鑫分离技术股份有限公司 | A kind of polyester fiber alkali processes the integrated conduct method of waste water |
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