CN108976400A - A kind of synthesis preparation method of the polyether high molecular compound of polyester containing zinc - Google Patents
A kind of synthesis preparation method of the polyether high molecular compound of polyester containing zinc Download PDFInfo
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- CN108976400A CN108976400A CN201810888534.0A CN201810888534A CN108976400A CN 108976400 A CN108976400 A CN 108976400A CN 201810888534 A CN201810888534 A CN 201810888534A CN 108976400 A CN108976400 A CN 108976400A
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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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/681—Polyesters containing atoms other than carbon, hydrogen and oxygen containing elements not provided for by groups C08G63/682 - C08G63/698
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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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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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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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/507—Polyesters
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
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Abstract
The invention discloses a kind of synthesis preparation methods of polyether high molecular compound of polyester containing zinc, its key points of the technical solution are that the steps include: the odd elements carboxylic acid that hydroxyl is added in the reaction vessel and reaction medium water；Then Zinc oxide powder is added to be stirred to react, obtains intermediate product hydroxycarboxylic acid zinc salt；Diglycol terephthalate is reacted to obtain intermediate product with hydroxycarboxylic acid zinc salt, dihydric alcohol, polycondensation reaction will be carried out under obtained intermediate product and terephthalic acid (TPA) dipropylene glycol ester, diglycol terephthalate, dihydric alcohol and poly-dihydric alcohol reduced pressure, obtains the polyether high molecular compound of polyester containing zinc of high molecular weight.The polyethers antistatic property of polyester containing zinc that the present invention synthesizes is excellent, and washability is good, significant to polyester fiber antistatic effect, while having good antibacterial effect.
Description
Technical field
The present invention relates to a kind of synthesis preparation methods of polyether high molecular compound of polyester containing zinc.
Background technique
Polyester fiber is big compared to natural fiber yield, has a wide range of application, with many excellent spies less than natural fiber
Property, but due to lacking hydrophilic radical in polyester fiber macromolecular, so that polyester fiber hydrophily is extremely low, in dry weather
Under the conditions of be easy to bring electrostatic accumulation because of friction, processing to polyester fiber and take and bring adverse effect.Therefore, terylene and its
The antistatic finish of blended fabric seems particularly necessary.
The antistatic agent applied in terylene final finishing processing is mostly the surfactant or macromolecule kind polyester of small molecule,
But the antistatic agent of these types is free of conductive metal ion, brought static elimination effect is limited, simultaneously because
Molecular weight is small, generally disposable antistatic treatment agent.There are also the polymer containing zinc to be synthesized, such as containing zinc
Esters of acrylic acid, the polyether ester amides containing zinc, polyester containing zinc.For example 201410246833.6 patent describes a kind of acrylic acid
The synthetic method of zinc resin, the zinc acrylate resin be applied to marine hull, coastal facility, submarine cable from polishing antifouling apply
Material.Another patent CN200810012834, describes a kind of preparation method of zinc-containing polyether ester amides, mainly uses aliphatic
Binary acid, polyethylene glycol, zinc oxide synthesize zinc-containing polyether ester amides with caprolactam performed polymer.Shaanxi Tech Univ congratulates precious member hair
In the paper " synthesis of metalline Hydrophilic Polyester Fiber fabric antistatic agent " of table, the synthesis of the polyester containing zinc is also described, mainly
Be with adipic acid, polyethylene glycol, zinc oxide, dimethyl terephthalate (DMT) it is raw material, synthesizes polyester containing zinc.But application this method is closed
At zinc-containing polyether ester, the reaction conversion ratio of intermediate polyester containing zinc it is low, white zinc oxide particle residue is obvious in final product.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide one kind can antistatic property it is excellent, it is resistance to
Washing property is good, significant to polyester fiber antistatic effect, while having the polyether high molecular of polyester containing zinc of good antibacterial effect
Close the synthesis preparation method of object.
To achieve the above object, the present invention provides the following technical scheme that a kind of polyether high molecular compound of polyester containing zinc
Synthesis preparation method, the steps include:
(1) the odd elements carboxylic acid and reaction medium water of hydroxyl are added in the reaction vessel；
(2) Zinc oxide powder is added when reaction vessel being heated to 30~50 DEG C, and the substance in reaction vessel is carried out
Stirring；
(3) reaction vessel is gradually warming up to 70~100 DEG C, 1~1.5h of isothermal reaction, it is decompressed to 0.001 later~
0.02MPa, pressure maintaining and constant pressure stop reaction after reacting 1~1.5h, obtain intermediate product hydroxycarboxylic acid zinc salt；
(4) intermediate product transfer, drying and mortar is finely ground stand-by；
(5) by diglycol terephthalate and step (4), treated that hydroxycarboxylic acid zinc salt is added empty reacts appearance
Device is reacted, and when reaction is passed through nitrogen protection, is stirred, and is warming up to 150~200 DEG C, and catalyst is added, and stops nitrogen protection,
It is decompressed to 0.001~0.02MPa, and constant temperature and pressure reacts 1~3h, obtains intermediate product, intermediate product is transferred out of reaction and is held
Device；
(6) intermediate product for obtaining step (5) and terephthalic acid (TPA) dipropylene glycol ester, terephthaldehyde's acid diethylene glycol
Ester, dihydric alcohol and poly-dihydric alcohol carry out polycondensation reaction, and when reaction is passed through nitrogen protection, stir, are warming up to 200 DEG C~280 DEG C, add
Enter catalyst, stop nitrogen protection, is decompressed to 0.001~0.02MPa, and constant temperature and pressure reacts 2.5~5h, is cooled to 120 DEG C
Lower taking-up product obtains the polyether high molecular compound of polyester containing zinc that high molecular weight is 5000~50000；
The present invention is further arranged to: according to step (1), the odd elements carboxylic acid of the hydroxyl is lactic acid, Alpha-hydroxy
One of butyric acid, beta-hydroxy-butanoic acid, gamma-hydroxybutyric acid and citric acid are a variety of.
The present invention is further arranged to: according to step (2), the zinc oxide is reacted with the odd elements carboxylic acid of hydroxyl
Molar ratio is carboxylic acid group number in odd elements carboxylic acid molecules that n: 2, n is hydroxyl, and n is odd number more than or equal to 1.
The present invention is further arranged to: according to step (5), the diglycol terephthalate and hydroxycarboxylic acid zinc
The molar ratio of salt is 2: 1~10: 1.
The present invention is further arranged to: according to step (6), the dihydric alcohol is ethylene glycol, 1,2-PD, 1,3- third
Glycol, 2- methyl-1,2- propylene glycol, 2- methyl-1,3-propanediol, 1,2- butanediol, 2,3-butanediol, 1,3-BDO, 1,
One of 4- butanediol is a variety of.
The present invention is further arranged to: according to step (6), the poly-dihydric alcohol be polyethylene glycol, poly- 1,2-PD,
One of polyoxyethylene oxypropylene block polyether, poly- 1,4-butanediol are a variety of.
The present invention is further arranged to: according to the polycondensation reaction in step (6), is produced from the centre that the step (5) obtains
The molar ratio of object and terephthalic acid (TPA) dipropylene glycol ester, diglycol terephthalate, dihydric alcohol and poly-dihydric alcohol is
(0.1~1): 5: 1: (1.5~2): (1.5~3)
The present invention is further arranged to: according to step (5) and (6), the catalyst is organic catalyst, organic titanium is urged
One of agent and organotin catalysts are a variety of, and the catalyst amount is 0.1~5 ‰.
The present invention is further arranged to: the organic catalyst is zinc acetate (ZnAc2), antimony acetate (SbAc3), three oxygen
Change two antimony (Sb2O3), the organotitanium is butyl titanate (TBT), tetraisopropyl titanate (TPT), metatitanic acid four are different pungent
Ester, four stearoylketene base titaniums, one bis-acetylacetonate base titanium of diisopropoxy, two n-butoxy a pair of (triethanolamine) titaniums, tributyl
Monoacylphosphine titanium, triisopropyl monoacylphosphine titanium, four titanium benzoates, the organotin catalysts are butyl stannonic acid (BSA), singly
Butyl tin oxide, stannous octoate, one diisooctyl tin of dibutyl, dimethyl tin oxide, Dibutyltin oxide, diphenyl oxidation
Tin, tributyl tin acetate, fluorination tributyl tin, triethyltin chloride, bromination tin triethyl, tin triethyl acetate, hydrogen-oxygen
Change tin trimethyl, triphenyltin chloride.
The present invention is further arranged to: according to step (2), (5) and (6), the mixing speed is 80~350rpm.
The present invention has an advantage that the present invention uses hydroxyl odd elements carboxylic acid, such as lactic acid, citric acid, hydroxyl
Acetic acid can be improved the acidity of the organic carboxyl acid reacted with zinc oxide, and reaction conversion ratio significantly improves, finally obtained macromolecule
The polyether resin appearance of polyester containing zinc is uniform, and is precipitated without white zinc oxide particle.The polyether resin of polyester containing zinc of synthesis is emulsified
And it is applied to terylene and blended fabric surface, the antistatic property of fabric is excellent and wash resistant, meanwhile, by antistatic finish
Terylene and blended fabric have excellent antibiotic property.
Contain metal zinc ion, polyether segment, phenyl ring segment, polyethers: phenyl ring: hydroxycarboxylic acid zinc salt mole in macromolecular chain
Than being 1: (3~6): (0.1~1), the structure and the molecular structure of terylene in polyester fiber are closest, therefore have to terylene excellent
Washable antistatic property.
The intermediate product reacted using hydroxycarboxylic acid zinc salt with diglycol terephthalate, with polyether Glycols, right
Phthalic acid diethyl/propylene glycol ester synthesizes the polyester polyether high molecular compound containing zinc, belongs to Hydrophilic nonionic producing high-molecular
Polymers, can be used emulsification method treatment fluid is made and be applied to fabric surface.Since there are conductivity type gold in polyester polyether high molecular
Belong to ion, can be used as durable antistatic inorganic agent, postfinishing process is to handle this macromolecule finishing agent by padding process
To dacron surface, shaping and drying.Polyester polyether high molecular compound metal ion zinc, antistatic property used in the present invention
Excellent, durability is good, significant to polyester fiber antistatic effect, while having good antibacterial effect.
Specific embodiment
A kind of synthesis preparation method of polyether high molecular compound of polyester containing zinc of the present embodiment, the steps include:
(1) the odd elements carboxylic acid and reaction medium water of hydroxyl are added in the reaction vessel；
(2) Zinc oxide powder is added when reaction vessel being heated to 30~50 DEG C, and the substance in reaction vessel is carried out
Stirring；
(3) reaction vessel is gradually warming up to 70~100 DEG C, 1~1.5h of isothermal reaction, it is decompressed to 0.001 later~
0.02MPa, pressure maintaining and constant pressure stop reaction after reacting 1~1.5h, obtain intermediate product hydroxycarboxylic acid zinc salt；
(4) intermediate product transfer, drying and mortar is finely ground stand-by；
(5) by diglycol terephthalate and step (4), treated that hydroxycarboxylic acid zinc salt is added empty reacts appearance
Device is reacted, and when reaction is passed through nitrogen protection, is stirred, and is warming up to 150~200 DEG C, and catalyst is added, and stops nitrogen protection,
It is decompressed to 0.001~0.02MPa, and constant temperature and pressure reacts 1~3h, obtains intermediate product, intermediate product is transferred out of reaction and is held
Device；
(6) intermediate product for obtaining step (5) and terephthalic acid (TPA) dipropylene glycol ester, terephthaldehyde's acid diethylene glycol
Ester, dihydric alcohol and poly-dihydric alcohol carry out polycondensation reaction, and when reaction is passed through nitrogen protection, stir, are warming up to 200 DEG C~280 DEG C, add
Enter catalyst, stop nitrogen protection, is decompressed to 0.001~0.02MPa, and constant temperature and pressure reacts 2.5~5h, is cooled to 120 DEG C
Lower taking-up product obtains the polyether high molecular compound of polyester containing zinc that high molecular weight is 5000~50000；
According to step (1), the odd elements carboxylic acid of the hydroxyl is lactic acid, alpha-hydroxybutyric acid, beta-hydroxy-butanoic acid, γ-
One of hydroxybutyric acid and citric acid are a variety of.
According to step (2), the zinc oxide is n: 2, n for containing hydroxyl with the molar ratio of reacting of the odd elements carboxylic acid of hydroxyl
Carboxylic acid group number in the odd elements carboxylic acid molecules of base, and n is the odd number more than or equal to 1.
According to step (5), the molar ratio of the diglycol terephthalate and hydroxycarboxylic acid zinc salt is 2: 1~10
∶1。
According to step (6), the dihydric alcohol is ethylene glycol, 1,2-PD, 1,3-PD, 2- methyl-1,2- third
Glycol, 2- methyl-1, one of 3-propanediol, 1,2- butanediol, 2,3-butanediol, 1,3-BDO, 1,4-butanediol or
It is a variety of.
According to step (6), the poly-dihydric alcohol is polyethylene glycol, poly- 1,2-PD, polyoxyethylene oxypropylene
One of block polyether, poly- 1,4-butanediol are a variety of.
According to the polycondensation reaction in step (6), intermediate product and terephthalic acid (TPA) dipropyl two that the step (5) obtains
Alcohol ester, diglycol terephthalate, dihydric alcohol and poly-dihydric alcohol molar ratio be (0.1~1): 5: 1: (1.5~2):
(1.5~3)
According to step (5) and (6), the catalyst is organic catalyst, organotitanium and organotin catalysts
One of or it is a variety of, the catalyst amount is 0.1~5 ‰.
The organic catalyst is zinc acetate (ZnAc2), antimony acetate (SbAc3), antimony oxide (Sb2O3), it is described
Organotitanium is butyl titanate (TBT), tetraisopropyl titanate (TPT), the different monooctyl ester of metatitanic acid four, four stearoylketene base titaniums, two
One bis-acetylacetonate base titanium of isopropoxy, two n-butoxy a pair of (triethanolamine) titaniums, tributyl monoacylphosphine titanium, triisopropyl
Monoacylphosphine titanium, four titanium benzoates, the organotin catalysts are butyl stannonic acid (BSA), Mono-n-butyltin, octanoic acid are sub-
Tin, one diisooctyl tin of dibutyl, dimethyl tin oxide, Dibutyltin oxide, diphenyl tin oxide, tributyl tin acetate,
It is fluorinated tributyl tin, triethyltin chloride, bromination tin triethyl, tin triethyl acetate, trimethyl tin hydroxide, chlorinated triphenyl
Ji Xi.
According to step (2), (5) and (6), the speed of the stirring is 80~350rpm.
Contain metal zinc ion, polyether segment, phenyl ring segment, polyethers: phenyl ring: hydroxycarboxylate's molar ratio in macromolecular chain
Be 1: (3~6): (0.1~1), the structure and the molecular structure of terylene in polyester fiber are closest, therefore have to terylene excellent
Washable antistatic property.
The macromolecule polyethers of polyester containing zinc of synthesis is emulsified, since the macromolecule contains a large amount of hydrophilic groups, can directly use water
Or nonionic emulsifier, anion emulsifier emulsify it, and solvent is added to reduce viscosity, after high pressure homogenizer
Emulsification product are made into the lotion of low-solid content.
It is made into antistatic working solution according to above-mentioned emulsion, fabrics of polyester is carried out to pad processing, antistatic agent concentration
For 2~6%soln, drying temperature is 100~160 DEG C, and drying time is 30s~5min.Measurement is washed the antibiotic property of preceding fabric, is resisted
Static behaviour；By fabric according to after standard wash 5 times, its antistatic property is measured.
Fabrics of polyester is pure polyester fabric, polyester fiber and natural fiber mixed textile fabric, and fabric specification is unlimited
In knitted fabric, woven fabric, nylon loop etc..
By using above-mentioned technical proposal, embodiment 1:
A certain amount of lactic acid and reaction medium water is added in the first step in four-hole boiling flask, and temperature rises to 30 DEG C, and oxidation is added
Zinc, lactic acid and zinc oxide molar ratio are 2: 1, continue to be heated to 70 DEG C, isothermal reaction was evacuated to 0.001MPa after two hours, made
Extra water steams, and place the product in low temperature drying in baking oven, steams moisture extra in zinc lactate sufficiently.
Step 2: being added in four-hole boiling flask a certain amount of by diglycol terephthalate, heating melting, to benzene two
Zinc lactate is added after the melting of formic acid binaryglycol ester, diglycol terephthalate and zinc lactate molar ratio 2: 1 lead to nitrogen
Gas, temperature rise to 180 DEG C, and the catalyst acetic acid zinc being dissolved in ethylene glycol at this time is added, and start to be evacuated to
Product is transferred out of four-hole boiling flask after 0.001MPa, constant pressure constant temperature 1.5h.
Step 3: walking reaction intermediate on being added in four-hole boiling flask, and add a certain amount of ethylene glycol, polyethylene glycol
4000, diglycol terephthalate, terephthalic acid (TPA) dipropylene glycol are added after melting, according to order of addition, 5 kinds of substances
Molar ratio is 0.5: 5: 1: 2: 2, is warming up to 120 DEG C, and catalyst acetic acid zinc is added, and is gradually heated to 200 DEG C, and catalyst Ti is added
Sour N-butyl is warming up to 240 DEG C and starts to vacuumize, and 0.001MPa is decompressed in 40min, and reacting after constant pressure constant temperature 2.5h terminates,
The uniform faint yellow dope of appearance is obtained, 120 DEG C of dischargings are cooled to.
Embodiment 2:
A certain amount of citric acid and reaction medium water is added in the first step in four-hole boiling flask, makes weak solution, temperature liter
To 40 DEG C, zinc oxide is added, citric acid and zinc oxide molar ratio are 2: 3, continue to be heated to 70 DEG C, isothermal reaction is taken out after two hours
Vacuum steams extra water, place the product in low temperature drying in baking oven, makes moisture extra in zinc citrate to 0.001MPa
Sufficiently steam.
Step 2: being added in four-hole boiling flask a certain amount of by diglycol terephthalate, heating melting, to benzene two
Zinc citrate is added after the melting of formic acid binaryglycol ester, diglycol terephthalate and zinc citrate molar ratio 2: 1 are led to
Nitrogen, temperature rise to 230 DEG C, and the catalyst acetic acid zinc being dissolved in ethylene glycol at this time is added, and start to be evacuated to
Product is transferred out of four-hole boiling flask after 0.001MPa, constant pressure constant temperature 1.5h.
Step 3: walking reaction intermediate on being added in four-hole boiling flask, and add a certain amount of ethylene glycol, polyethylene glycol
4000, diglycol terephthalate, terephthalic acid (TPA) dipropylene glycol are added after melting, according to order of addition, 5 kinds of substances
Molar ratio is 0.5: 5: 1: 2: 2, is warming up to 120 DEG C, and catalyst acetic acid zinc is added, and is gradually heated to 200 DEG C, and catalyst Ti is added
Sour N-butyl is warming up to 240 DEG C and starts to vacuumize, and 0.001MPa is decompressed in 40min, and reacting after constant pressure constant temperature 2.5h terminates,
The uniform faint yellow dope of appearance is obtained, 120 DEG C of dischargings are cooled to.
Reference case:
A certain amount of citric acid and reaction medium water is added in the first step in four-hole boiling flask, and temperature rises to 30 DEG C, and oxidation is added
Zinc, citric acid and zinc oxide molar ratio are 2: 1, continue to be heated to 70 DEG C, and isothermal reaction was evacuated to 0.001MPa after two hours,
The water in reaction system is steamed, place the product in low temperature drying in baking oven, steams moisture extra in zinc citrate sufficiently.
Step 2: Macrogol 4000 is added in four-hole boiling flask, the zinc citrate for walking preparation is added after melting, stirs
It mixes, adds ethylene glycol, diglycol terephthalate, terephthalic acid (TPA) dipropylene glycol ester, according to order of addition, participate in anti-
The molar ratio for the 5 kinds of substances answered is 1: 0.5: 5: 3: 2, is warming up to 120 DEG C, and catalyst acetic acid zinc is added, is gradually heated to 200
DEG C, there is the small insoluble matter of white, catalyst tetrabutyl titanate is added, is increased with temperature, white insoluble matter gradually increases, heating
Start to depressurize when to 240 DEG C, during being decompressed to 0.001MPa, as pressure constantly reduces in reaction vessel, occur a large amount of
Cotton-shaped floating material cannot be eliminated as reaction carries out cotton-shaped floating material, stop reaction, obtained production after constant pressure isothermal reaction 2.5h
Object is inhomogenous, and appearance has white particle with a large amount of.
Embodiment 3:
The macromolecule polyethers of polyester containing zinc of synthesis is emulsified, takes 100g macromolecule to be placed in flask and melts, be added after melting
Nonionic emulsifier, anion emulsifier are added 30g solvent 2- ethylene glycol monobutyl ether, are slowly added into the water not higher than 60 DEG C and stir
It mixes, obtains emulsion 1000g, cross high pressure homogenizer to reduce the viscosity of lotion, finally obtain the lotion of 10% solid content, as
Antistatic agent containing zinc；
Above-mentioned part is the preparation embodiment of antistatic agent, below with specific application example to the performance antistatic containing zinc
Effect is illustrated.Fabric antistatic property test method reference standard JIS L1094:2008 before washing and after washing is charged by friction
Measuring method and half-life period measuring method is pressed to carry out (experimental enviroment condition: 20 ± 2 DEG C, 40 ± 2%RH).Washing methods refers to JIS
103 method of L0217 is washed 5 times, hereinafter washes statement with " L5 ", with " L0 " statement before washing.Wash the antibacterial test reference expected front
2008 quantitative test of antibacterial test JIS L1902 (bacterium solution absorption process) of fiber product carries out, net bacterium activity value > 2.2
For with good antibacterial effect；
Embodiment 4:
Antistatic agent containing zinc is diluted to the aqueous solution of 4% mass percent, red woven polyester cloth is carried out padding place
Reason, drying temperature are 120 DEG C, and drying time is 2~3min.Treated fabric according to after standard wash 5 times, measure its resist it is quiet
Electrical property and wash preceding anti-microbial property.
Fabric after using antistatic agent containing zinc to process is evaluated, net bacterium activity value > 5.8, antibacterial effect is good.
It was 10V (cotton), 20V (hair), half-life period less than 1 second that L0, which is charged by friction pressure, before washing, L5 wash after be charged by friction pressure be 570V (cotton),
1270V (hair), half-life period are 2 seconds.
Unprocessed red PET woven fabric is evaluated, net bacterium activity value is 1.2, and antibacterial effect is poor.Initial stage, L0 rubbed
Wiping with voltage is 3000V (cotton), 4700V (hair), and half-life period is greater than 120 seconds.L5 wash after be charged by friction pressure be 4400V (cotton),
5200V (hair), half-life period are greater than 120 seconds.
To the red for using the processing of polyester polyether resin NICEPOLE PR-99 same process similar in the structure without zinc
Woven fabric is evaluated, and net bacterium activity value is 1.2, and antibacterial effect is poor.It is 130V (cotton), 120V that L0, which is charged by friction pressure, before washing
(hair), half-life period less than 1 second, L5 wash after be charged by friction that pressure is 1380V (cotton), 2370V (hair), half-life period are 29 seconds；
Embodiment 5:
Antistatic agent containing zinc is diluted to the aqueous solution of 4% mass percent, terylene camouflage cotton flannel is padded
Processing, drying temperature are 120 DEG C, and drying time is 3~5min.Treated, and fabric is anti-according to it after standard wash 5 times, is measured
Antistatic property.
To use antistatic agent containing zinc process after fabric evaluate, wash before L0 be charged by friction pressure be 150V (cotton),
240V (hair), half-life period less than 1 second, L5 wash after be charged by friction that pressure is 1500V (cotton), 2600V (hair), half-life period are 2 seconds.
Unprocessed terylene camouflage cotton flannel is evaluated, it is 4000V (cotton), 4700V that initial stage L0, which is charged by friction pressure,
(hair), half-life period are greater than 120 seconds.The pressure that is charged by friction after L5 is washed is greater than 120 seconds for 4800V (cotton), 5500V (hair), half-life period.
To the terylene for using the processing of polyester polyether resin NICEPOLE PR-99 same process similar in the structure without zinc
Camouflage color cotton flannel is evaluated, and it was 330V (cotton), 720V (hair), half-life period less than 1 second that L0, which is charged by friction pressure, before washing, after L5 is washed
Be charged by friction that pressure is 3600V (cotton), 4400V (hair), half-life period are 65 seconds.
The above is only a preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-mentioned implementation
Example, all technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It should be pointed out that for the art
Those of ordinary skill for, several improvements and modifications without departing from the principles of the present invention, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of synthesis preparation method of the polyether high molecular compound of polyester containing zinc, it is characterised in that: the steps include:
(1) the odd elements carboxylic acid and reaction medium water of hydroxyl are added in the reaction vessel；
(2) Zinc oxide powder is added when reaction vessel being heated to 30~50 DEG C, and the substance in reaction vessel is stirred；
(3) reaction vessel is gradually warming up to 70~100 DEG C, 1~1.5h of isothermal reaction, it is decompressed to 0.001 later~
0.02MPa, pressure maintaining and constant pressure stop reaction after reacting 1~1.5h, obtain intermediate product hydroxycarboxylic acid zinc salt；
(4) intermediate product transfer, drying and mortar is finely ground stand-by；
(5) by treated diglycol terephthalate and step (4) hydroxycarboxylic acid zinc salt is added empty reaction vessel into
Row reaction, when reaction, are passed through nitrogen protection, stir, and are warming up to 150~200 DEG C, and catalyst is added, and stop nitrogen protection, decompression
To 0.001~0.02MPa, and constant temperature and pressure reacts 1~3h, obtains intermediate product, intermediate product is transferred out of reaction vessel；
(6) intermediate product for obtaining step (5) and terephthalic acid (TPA) dipropylene glycol ester, diglycol terephthalate, two
First alcohol and poly-dihydric alcohol carry out polycondensation reaction, and when reaction is passed through nitrogen protection, stir, are warming up to 200 DEG C~280 DEG C, addition is urged
Agent stops nitrogen protection, is decompressed to 0.001~0.02MPa, and constant temperature and pressure reacts 2.5~5h, is cooled at 120 DEG C and takes
Product out obtains the polyether high molecular compound of polyester containing zinc that high molecular weight is 5000~50000.
2. a kind of synthesis preparation method of polyether high molecular compound of polyester containing zinc according to claim 1, feature exist
In: according to step (1), the odd elements carboxylic acid of the hydroxyl is lactic acid, alpha-hydroxybutyric acid, beta-hydroxy-butanoic acid, γ-hydroxyl fourth
One of acid and citric acid are a variety of.
3. a kind of synthesis preparation method of polyether high molecular compound of polyester containing zinc according to claim 1, feature exist
In: according to step (2), the molar ratio of reacting of the zinc oxide and the odd elements carboxylic acid of hydroxyl be n: 2, n is hydroxyl
Carboxylic acid group number in odd elements carboxylic acid molecules, and n is the odd number more than or equal to 1.
4. a kind of synthesis preparation method of polyether high molecular compound of polyester containing zinc according to claim 1, feature exist
In: according to step (5), the molar ratio of the diglycol terephthalate and hydroxycarboxylic acid zinc salt is 2: 1~10: 1.
5. a kind of synthesis preparation method of polyether high molecular compound of polyester containing zinc according to claim 1, feature exist
In: according to step (6), the dihydric alcohol is ethylene glycol, 1,2-PD, 1,3-PD, 2- methyl-1,2- propylene glycol,
2- methyl-1, one of 3-propanediol, 1,2- butanediol, 2,3-butanediol, 1,3-BDO, 1,4-butanediol or a variety of.
6. a kind of synthesis preparation method of polyether high molecular compound of polyester containing zinc according to claim 1, feature exist
In: according to step (6), the poly-dihydric alcohol is polyethylene glycol, poly- 1,2-PD, polyoxyethylene oxypropylene block are poly-
One of ether, poly- 1,4-butanediol are a variety of.
7. a kind of synthesis preparation method of polyether high molecular compound of polyester containing zinc according to claim 1, feature exist
In: according to the polycondensation reaction in step (6), intermediate product that the step (5) obtains and terephthalic acid (TPA) dipropylene glycol ester,
The molar ratio of diglycol terephthalate, dihydric alcohol and poly-dihydric alcohol is (0.1~1): 5: 1: (1.5~2): (1.5~
3)。
8. a kind of synthesis preparation method of polyether high molecular compound of polyester containing zinc according to claim 1, feature exist
In: according to step (5) and (6), the catalyst is one in organic catalyst, organotitanium and organotin catalysts
Kind is a variety of, and the catalyst amount is 0.1~5 ‰.
9. a kind of synthesis preparation method of polyether high molecular compound of polyester containing zinc according to claim 8, feature exist
In: the organic catalyst is zinc acetate (ZnAc2), antimony acetate (SbAc3), antimony oxide (Sb2O3), described is organic
Titanium catalyst is butyl titanate (TBT), tetraisopropyl titanate (TPT), the different monooctyl ester of metatitanic acid four, four stearoylketene base titaniums, diisopropyl
One bis-acetylacetonate base titanium of oxygroup, two n-butoxy a pair of (triethanolamine) titaniums, tributyl monoacylphosphine titanium, triisopropyl list second
Acyl group titanium, four titanium benzoates, the organotin catalysts are butyl stannonic acid (BSA), Mono-n-butyltin, stannous octoate, two
One diisooctyl tin of butyl, dimethyl tin oxide, Dibutyltin oxide, diphenyl tin oxide, tributyl tin acetate, fluorination three
Butyl tin, triethyltin chloride, bromination tin triethyl, tin triethyl acetate, trimethyl tin hydroxide, triphenyltin chloride.
10. a kind of synthesis preparation method of polyether high molecular compound of polyester containing zinc according to claim 1, feature exist
In: according to step (2), (5) and (6), the speed of the stirring is 80~350rpm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111893767A (en) * | 2020-07-29 | 2020-11-06 | 日华化学（中国）有限公司 | Durable antistatic agent for polyester fabric and preparation method of polyester antistatic fabric |
| CN111978522A (en) * | 2020-09-08 | 2020-11-24 | 常州美胜生物材料有限公司 | Preparation method of hydrophilic antistatic antibacterial copolyester master batch |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348566A (en) * | 2008-08-15 | 2009-01-21 | 大连工业大学 | Preparation of zinc-containing polyether ester amides |
| CN106087427A (en) * | 2016-06-14 | 2016-11-09 | 东华大学 | A kind of antistatic, the preparation method of flame-retarding uniforms for worker fabric |
-
2018
- 2018-08-07 CN CN201810888534.0A patent/CN108976400B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348566A (en) * | 2008-08-15 | 2009-01-21 | 大连工业大学 | Preparation of zinc-containing polyether ester amides |
| CN106087427A (en) * | 2016-06-14 | 2016-11-09 | 东华大学 | A kind of antistatic, the preparation method of flame-retarding uniforms for worker fabric |
Non-Patent Citations (3)
| Title |
|---|
| 贺宝元: "亲水性非离子型抗静电剂的合成及应用性能的研究", 《印染助剂》 * |
| 贺宝元: "含金属盐亲水性涤纶织物抗静电剂的合成", 《日用化学工业》 * |
| 郭静: "高分子抗静电剂—含锌聚醚酯酰胺的合成与表征", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111893767A (en) * | 2020-07-29 | 2020-11-06 | 日华化学（中国）有限公司 | Durable antistatic agent for polyester fabric and preparation method of polyester antistatic fabric |
| CN111978522A (en) * | 2020-09-08 | 2020-11-24 | 常州美胜生物材料有限公司 | Preparation method of hydrophilic antistatic antibacterial copolyester master batch |
| CN111978522B (en) * | 2020-09-08 | 2022-12-20 | 常州美胜生物材料有限公司 | Preparation method of hydrophilic antistatic antibacterial copolyester master batch |
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