CN106831430A - Etherificate gaultherolin and its product, application - Google Patents

Etherificate gaultherolin and its product, application Download PDF

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Publication number
CN106831430A
CN106831430A CN201710052612.9A CN201710052612A CN106831430A CN 106831430 A CN106831430 A CN 106831430A CN 201710052612 A CN201710052612 A CN 201710052612A CN 106831430 A CN106831430 A CN 106831430A
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China
Prior art keywords
gaultherolin
accelerant
terylene
acid
red
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Granted
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CN201710052612.9A
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CN106831430B (en
Inventor
徐光润
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Zhejiang Huasheng Textile Technology Co.,Ltd.
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Jia Xinghua Sheng Assistant Industrial Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/84—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring
    • C07C69/92—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring with etherified hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
    • C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/83—Chemically modified polymers
    • C08G18/831—Chemically modified polymers by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/60—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
    • D06P1/613—Polyethers without nitrogen
    • D06P1/6131—Addition products of hydroxyl groups-containing compounds with oxiranes
    • D06P1/6133—Addition products of hydroxyl groups-containing compounds with oxiranes from araliphatic or aliphatic alcohols
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/60—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
    • D06P1/613—Polyethers without nitrogen
    • D06P1/6131—Addition products of hydroxyl groups-containing compounds with oxiranes
    • D06P1/6135—Addition products of hydroxyl groups-containing compounds with oxiranes from aromatic alcohols or from phenols, naphthols
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/60—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
    • D06P1/613—Polyethers without nitrogen
    • D06P1/6136—Condensation products of esters, acids, oils, oxyacids with oxiranes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/651—Compounds without nitrogen
    • D06P1/65106—Oxygen-containing compounds
    • D06P1/65125—Compounds containing ester groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/651—Compounds without nitrogen
    • D06P1/65106—Oxygen-containing compounds
    • D06P1/65131—Compounds containing ether or acetal groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/673—Inorganic compounds
    • D06P1/67383—Inorganic compounds containing silicon
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/34—Material containing ester groups
    • D06P3/52—Polyesters

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Detergent Compositions (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The present invention relates to textile printing and dyeing field, and in particular to one kind etherificate gaultherolin and its product, application.The etherificate gaultherolin, the etherificate gaultherolin at least includes that gaultherolin or gaultherolin derivative, etherifying reagent are obtained by etherification reaction；The etherifying reagent is selected from any one in epoxies etherifying reagent or alcohols etherifying reagent.

Description

Etherificate gaultherolin and its product, application
Technical field
The present invention relates to textile printing and dyeing field, and in particular to one kind etherificate gaultherolin and its product, application.
Background technology
Traditional gaultherolin, methyl naphthalene, phthalate product has as first generation dyeing terylene accelerant Long history, later due to smell and the requirement of environmental protection, gradually by the smaller color yield of part smell product higher such as：Benzene Benzyl formate, phenol benzoate, the substitution of benzoic acid alkoxide product；As market is to the even more important and harshness of odor requirements, Slowly main nearly tasteless polyol ester, the substitution of phthalimide class product, polyol ester, color yield is low, to blending The staining of fiber is serious, and pure color degree is bad, and color fastness is also poor, phthalimide pure color, good color fastness, but Color rate is low, and high cost, staining are serious, and cost is very high, it is difficult to widely use.Thus, it is also very desirable to by technique and formula Improve to develop a multi-functional textile auxiliary.
The content of the invention
In order to solve prior art problem, first aspect present invention provides a kind of etherificate gaultherolin, the etherificate water Poplar acid methyl esters at least includes that gaultherolin or gaultherolin derivative, etherifying reagent are obtained by etherification reaction；
The etherifying reagent is selected from any one in epoxies etherifying reagent or alcohols etherifying reagent.
In a preferred embodiment, the epoxies etherifying reagent is selected from：Oxirane, expoxy propane, epoxy In butane, 1,2- cyclopentane epoxides, oxepane, 1,2- oxepanes, 2- octylene oxides, decamethylene any one or it is several The combination planted.
In a preferred embodiment, the alcohols etherifying reagent is selected from：Ethylene glycol, diethylene glycol, propane diols, fourth Glycol, pentanediol, ethylene glycol, glycerine, polyvinyl alcohol, polyethylene glycol, cyclodextrin, shitosan, hydroxy-end capped hyperbranched poly ammonia Any one or a few combination in ester.
The second aspect of the invention provides the preparation method of the etherificate gaultherolin, at least including following step Suddenly：
Gaultherolin or gaultherolin derivative, etherifying reagent are dissolved in organic solvent as reaction system, then are added Enter the dilute sulfuric acid that mass fraction is 1%, wherein, the weight of dilute sulfuric acid is the 30% of gaultherolin or gaultherolin derivative ~60%, by reaction system at 50~100 DEG C, 3~7h is reacted, obtain being etherified gaultherolin.
In a preferred embodiment, the gaultherolin or gaultherolin derivative and etherifying reagent rub You are than being 1：1~3.
The third aspect of the invention provide a kind of terylene accelerant, the terylene accelerant, in parts by weight, at least Including：
100 parts of nonionic surfactant；
1~8 part of gaultherolin of etherificate；
Wherein, the nonionic surfactant at least includes fatty alcohol ether, cithrol, styryl benzene Phenol polyethenoxy ether.
In a preferred embodiment, the fatty alcohol ether, cithrol, styrylphenol polyoxy Weight ratio between vinethene is 1：10：10~100.
In a preferred embodiment, the nano-silica of 0.1~0.5 weight portion is also included in the terylene accelerant SiClx.
The fourth aspect of the invention provides the preparation method of the terylene accelerant, at least comprises the following steps：
After material is mixed, be warming up to 50~80 DEG C, under 60~120r/min speed stir 1~2 hour, after be cooled to 30~40 DEG C, discharging obtains terylene accelerant.
The fifth aspect of the invention provides etherificate gaultherolin in textile printing and dyeing, plasticizer, flavouring agent field Using.
Specific embodiment
The participation in the election detailed description for being preferable to carry out method of the invention below and including embodiment this hair can be more easily understood Bright content.Unless otherwise defined, all technologies used herein and scientific terminology have common with art of the present invention The identical implication that technical staff is generally understood that.When there is contradiction, the definition in this specification is defined.
As used herein term " by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " including ", " having ", " containing " or its any other deformation, it is intended that cover including for non-exclusionism.For example, the combination comprising listed elements Thing, step, method, product or device are not necessarily limited to those key elements, and can be including not expressly listed other key elements or This kind of composition, step, method, product or the intrinsic key element of device.
Conjunction " Consists of " excludes any key element do not pointed out, step or component.If be used in claim, this Phrase will make claim be closed, it is not included the material in addition to the material that those are described, but relative normal Except rule impurity.When phrase " Consists of " is appeared in be rather than immediately following after theme in the clause of claim main body, It is only limited to the key element described in the clause；Other key elements are not excluded outside as the overall claim.
Equivalent, concentration or other values or parameter are excellent with scope, preferred scope or a series of upper limit preferred values and lower limit During the Range Representation that choosing value is limited, this is appreciated that and specifically discloses by any range limit or preferred value and any scope All scopes that any pairing of lower limit or preferred value is formed, regardless of whether whether the scope separately discloses.For example, when open During scope " 1 to 5 ", described scope should be interpreted as including scope " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to 5 ", " 1 to 3 and 5 " etc..When number range is described herein, unless otherwise indicated, otherwise the scope is intended to include its end Value and all integers and fraction within the range.
Singulative includes that plural number discusses object, unless the context clearly dictates otherwise.It is " optional " or " any It is a kind of " refer to that the item that describes thereafter or event may or may not occur, and the description include situation that event occurs and The situation that event does not occur.
Approximate term in specification and claims is used for modifying quantity, represents that the present invention is not limited to this specific Quantity, also including the acceptable part without cause the amendment of the change of related basic function close to the quantity.Phase Answer, a numerical value is modified with " about ", " about " etc., mean the invention is not restricted to the exact numerical.In some examples, approximately Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, scope is limited can be with Combine and/or exchange, these scopes include all subranges contained therebetween if not stated otherwise.
Additionally, the indefinite article " one kind " and " one " before key element of the present invention or component are to key element or the quantitative requirement of component (i.e. occurrence number) unrestriction.Therefore " one " or " one kind " should be read as including one or at least one, and odd number The key element or component of form also include plural form, unless the obvious purport of the quantity refers to singulative.
In order to solve prior art problem, first aspect present invention provides a kind of etherificate gaultherolin, the etherificate water Poplar acid methyl esters at least includes that gaultherolin or gaultherolin derivative, etherifying reagent are obtained by etherification reaction；
The etherifying reagent is selected from any one in epoxies etherifying reagent or alcohols etherifying reagent.
Gaultherolin
" gaultherolin " of the present invention had both included gaultherolin or including gaultherolin derivative.
Etherifying reagent
In the present invention, the etherifying reagent is selected from any one in epoxies etherifying reagent or alcohols etherifying reagent.
What the epoxies etherifying reagent can be enumerated has：Oxirane, expoxy propane, epoxy butane, 1,2- epoxide rings Pentane, oxepane, 1,2- oxepanes, 2- octylene oxides, decamethylene, epoxidized soybean oil, epoxy Linseed oil, 4,5- rings Oxygen diisodecyl tetrahydrophthalate, 4,5- epoxies tetrahydrophthalic acid two (2- ethyl hexyls) ester, butyl epoxy stearate, Epoxystearic acid 2- Octyl Nitrites, the different monooctyl ester of epoxystearic acid, epoxidized tall oil acid 2- Octyl Nitrites, epoxy soybean oleic acid 2- second In the own ester of base, epoxidized methyl acetorieinoleate, epoxy pupal fat acid butyl ester, epoxyfuoic-oleic, epoxidation triglyceride Any one.
In a preferred embodiment, the epoxies etherifying reagent is selected from：Oxirane, expoxy propane, epoxy Any one in butane, 1,2- cyclopentane epoxides, oxepane, 1,2- oxepanes, 2- octylene oxides, decamethylene.
What the alcohols etherifying reagent can be enumerated has：Ethylene glycol, diethylene glycol, propane diols, butanediol, pentanediol, second Any one in glycol, glycerine, polyvinyl alcohol, polyethylene glycol, cyclodextrin, shitosan, hydroxy-end capped super branched polyurethane.
In a preferred embodiment, the alcohols etherifying reagent is selected from：Ethylene glycol, diethylene glycol, propane diols, fourth Glycol, pentanediol, ethylene glycol, glycerine, polyvinyl alcohol, polyethylene glycol, cyclodextrin, shitosan, hydroxy-end capped hyperbranched poly ammonia Any one in ester.
The second aspect of the invention provides the preparation method of the etherificate gaultherolin, at least including following step Suddenly：
Gaultherolin or gaultherolin derivative, etherifying reagent are dissolved in organic solvent as reaction system, then are added Enter the dilute sulfuric acid that mass fraction is 1%, wherein, the weight of dilute sulfuric acid is the 30% of gaultherolin or gaultherolin derivative ~60%, by reaction system at 20~50 DEG C, 3~7h is reacted, obtain being etherified gaultherolin.
In a preferred embodiment, the gaultherolin or gaultherolin derivative and etherifying reagent rub You are than being 1：1~3.
In the present invention, as long as the organic solvent for being used can dissolve reactant, the organic solvent can be arranged That lifts has：Chlorinated hydrocarbon, alkane, ethers, ketone, esters, in the combination of one or more.
What the chlorinated hydrocarbon organic solvent can illustrate has：Chloroform, chloroform, dichloropropane etc..
What the alkanes organic solvent can illustrate has：Hexamethylene, n-hexane, normal heptane, normal octane etc..
What the ether organic solvent can illustrate has：Tetrahydrofuran, dioxane etc..
What the organic solvent of ketone can illustrate has：Diisopropyl ketone, hexone etc..
What the based organic solvent can illustrate has：Isobutyl acetate, ethyl acetate etc..
Other：Dimethyl sulfoxide (DMSO), methyl alcohol, ethanol, propyl alcohol etc..
In a preferred embodiment, the etherifying reagent is expoxy propane, the system of the etherificate gaultherolin Preparation Method is：
Gaultherolin, expoxy propane are dissolved in dimethyl sulfoxide (DMSO) as reaction system, wherein, gaultherolin, ring Ethylene Oxide, the mol ratio of dimethyl sulfoxide (DMSO) are 1：1：40.The dilute sulfuric acid that mass fraction is 1% is added, wherein, the weight of dilute sulfuric acid It is the 30% of gaultherolin to measure, and by reaction system at 60 DEG C, reacts 7h, obtains being etherified gaultherolin.
In a preferred embodiment, the etherifying reagent is polyethylene glycol, the system of the etherificate gaultherolin Preparation Method is：
Gaultherolin, polyethylene glycol are dissolved in absolute ethyl alcohol as reaction system, wherein, gaultherolin, poly- second Glycol, the mol ratio of absolute ethyl alcohol are 1：1：50.The dilute sulfuric acid that mass fraction is 1% is added, wherein, the weight of dilute sulfuric acid is The 20% of gaultherolin, by reaction system at 100 DEG C, reacts 7h, obtains being etherified gaultherolin.
In a preferred embodiment, the etherifying reagent is cyclodextrin, the preparation of the etherificate gaultherolin Method is：
Gaultherolin, cyclodextrin are dissolved in dimethyl sulfoxide (DMSO) as reaction system, wherein, gaultherolin, ring paste Essence, the mol ratio of dimethyl sulfoxide (DMSO) are 1：1：30.The dilute sulfuric acid that mass fraction is 1% is added, wherein, the weight of dilute sulfuric acid is The 20% of gaultherolin, by reaction system at 100 DEG C, reacts 7h, obtains being etherified gaultherolin.
Cyclodextrin of the present invention can be cyclodextrin, or cyclodextrine derivatives.
Described cyclodextrin and cyclodextrine derivatives such as, but not limited to, cyclodextrin such as alpha-cyclodextrin, beta-schardinger dextrin and Gamma-cyclodextrin；Cyclodextrine derivatives such as Dimethyl cyclodextrin, glucose cyclodextrin, 2- the Hydroxyproply-α-cyclodextrins ,-O- of 2,6- bis- Methyl-alphacyclodextrin, 6-O- α-malt-base-alpha-cyclodextrin, 6-O- α-D- glucityls-alpha-cyclodextrin, the six (- O- of 2,3,6- tri- Acetyl group)-alpha-cyclodextrin, the six (- O- methyl of 2,3,6- tri-)-alpha-cyclodextrins, six (6-O- tosyls)-alpha-cyclodextrins, six (6- amino -6- deoxidations)-alpha-cyclodextrin, six (the bromo- 6- deoxidations of 2,3- acetyl group -6-)-alpha-cyclodextrins, six (- the O- of 2,3,6- tri- are pungent Base)-alpha-cyclodextrin, list (2-O- phosphoryls)-alpha-cyclodextrin, list [2, (3)-O- (carboxymethyl)]-alpha-cyclodextrin, eight (uncles 6-O- Butyldimethylsilyl)-alpha-cyclodextrin, succinyl-alpha-cyclodextrin, glucuronyl- glucose group-beta-cyclodextrin, seven (2, - O- the methyl of 6- bis-)-beta-schardinger dextrin, the seven (- O- ethyls of 2,6- bis-)-beta-schardinger dextrins, seven (6-O- sulfo groups)-beta-schardinger dextrins, seven (2, - O- acetyl group -6-O- the sulfo groups of 3- bis-)-beta-schardinger dextrin, the seven (- O- methyl -6-O- sulfo groups of 2,3- bis-)-beta-schardinger dextrins, seven (2,3, - O- the acetyl group of 6- tri-)-beta-schardinger dextrin, the seven (- O- benzoyls of 2,3,6- tri-)-beta-schardinger dextrins, the seven (- O- methyl of 2,3,6- tri-)- Beta-schardinger dextrin, the seven (- O- methyl of 3-O- acetyl group -2,6- two)-beta-schardinger dextrins, seven (the bromo- 6- deoxidations of 2,3-O- acetyl group -6-) - Beta-schardinger dextrin, 2- hydroxyethyl-β-cyclodextrins, HP-β-CD, 2-HP-BETA-CD, (2- hydroxyls -3-N, N, N- Dimethylamino) propyl-beta-cyclodextrin, 6-O- α-malt sugar group-beta-cyclodextrin, methyl-B-cyclodextrin, six (6- amino -6- take off Oxygen)-beta-schardinger dextrin, double (6- nitrine -6- deoxidations)-beta-schardinger dextrins, list (2-O- phosphoryls)-beta-schardinger dextrin, six [6- deoxidations -6- (1- imidazole radicals)]-beta-schardinger dextrin, single acetyl group-beta-cyclodextrin, triacetyl group-beta-cyclodextrin, monochloro triazine group-beta-cyclodextrin, 6-O- α-D- glucose group-beta-cyclodextrin, 6-O- α-D-Maltose group-beta-cyclodextrin, succinyl-beta-cyclodextrin, succinyl-(2- Hydroxypropyl)-beta-schardinger dextrin, 2- carboxymethyl-beta-cyclodextrins, 2- carboxyethyls-beta-schardinger dextrin, fourth group-beta-cyclodextrin, sulfopropyl-β- Cyclodextrin, 6- monodeoxy -6- monoamines group-beta-cyclodextrin, the silicyl [- O- acetyl of (6-O- fert-butyidimethylsilyls) 2,3- bis- Base]-beta-schardinger dextrin, 2- ethoxys-gamma-cyclodextrin, 2- hydropropyl-y-cyclodextrins, butyl-gamma-cyclodextrin, 3A- amino -3A- Deoxidation-(2AS, 3AS)-gamma-cyclodextrin, list -2-O- (p-toluenesulfonyl)-gamma-cyclodextrin, list -6-O- (tolysulfonyl Base)-gamma-cyclodextrin, list -6-O- mesitylene sulfonyl-gamma-cyclodextrin, the eight (- O- methyl of 2,3,6- tri-)-gamma-cyclodextrins, The eight (- O- phenyl of 2,6- bis-)-gamma-cyclodextrins, eight (6-O- t-butyldimethylsilyls)-gamma-cyclodextrins and eight (2,3,6- Three-O- acetyl group)-gamma-cyclodextrin.
In a preferred embodiment, the etherifying reagent is hydroxy-end capped super branched polyurethane, the etherificate water Poplar acid methyl esters preparation method be：
Gaultherolin, hydroxy-end capped super branched polyurethane are dissolved in dimethyl sulfoxide (DMSO) as reaction system, wherein, water Poplar acid methyl esters, hydroxy-end capped super branched polyurethane, the mol ratio of dimethyl sulfoxide (DMSO) are 1：1：30.It is 1% to add mass fraction Dilute sulfuric acid, wherein, the weight of dilute sulfuric acid is the 20% of gaultherolin, by reaction system at 100 DEG C, reacts 7h, is obtained Etherificate gaultherolin.
The preparation method specific steps of hydroxy-end capped super branched polyurethane：3 grams of pentaerythrites (PER) are taken with 20 grams of N, N- bis- NMF (DMF) dissolves, and obtains terminal hydroxy group small molecule polyol solution.By 11.67 grams of IPDIs (IPDI) 90 DEG C are heated to, terminal hydroxy group small molecule polyol solution stirring reaction is added 6 hours, the hyperbranched pre-polymerization of the first generation is obtained Thing a1.By 34.67 grams of first generation hyper-branched prepolymers a110 DEG C are cooled to 20 grams of diethanol amine, blending reaction 6 hours are incubated, Products therefrom is vacuum dried with after water separating-purifying, obtains hydroxy-end capped super branched polyurethane.
The third aspect of the invention provide a kind of terylene accelerant, the terylene accelerant, in parts by weight, at least Including：
100 parts of nonionic surfactant；
1~8 part of gaultherolin of etherificate；
Wherein, the nonionic surfactant at least includes fatty alcohol ether, cithrol, styryl benzene Phenol polyethenoxy ether.
Nonionic surfactant
In the present invention, the nonionic surfactant at least includes fatty alcohol ether, cithrol, styrene The mixing of one or more in base phenol APEO.
In the present invention, the fatty alcohol ether is mainly polyoxyalkylene fatty alcohol ether.
Polyoxyalkylene fatty alcohol ether is also referred to as polyoxyalkylene alkyl, is generally expressed from the next：R-O- (AO) nH, wherein R It is alkenyl, (AO) n is polyoxyethylene, polyoxypropylene or polyoxyethylene polyoxypropylene block copolymer, and n is 2~30.
The polyoxyalkylene fatty alcohol ether that can be enumerated, including but not limited to, polyoxyethylene lauryl ether, polyoxethylene octylphenyl Ether, polyoxyethylene myristyl ether, polyoxyethylene stearyl base ether and polyoxyethylene oleyl ether.They pass through oxyalkylene (such as ring Oxidative ethane, expoxy propane) prepared to the addition of fatty alcohol, the fatty alcohol is C1-C22Aliphatic alcohol.
Polyethylene glycols fatty acid ester is divided into monoesters and dibasic acid esters.The aliphatic acid prepared for it typically laurate, oleic acid Deng；Polyethylene glycol (PEG) is the product of ethers, chemical molecular formula HO (CH2CH2O) nH, its molecular weight is from 200~20000.Poly- second With the increase of its molecular weight, its outward appearance is presented the physical property of glycol at room temperature is colourless, odorless transparency liquid to faint yellow Waxy solid；Its is stable in properties, although be high polymer, but with preferable water solubility.
Industrial PEG is with ethylene glycol or oxirane as raw material, in addition polymerization system in polymeric kettle under the catalysis of alkali Standby.The synthetic method of usual PEG fatty acid ester activating agents mainly has ethyoxyl method, the step alcoholysis method of phthalein chlorine two, direct esterification. Wherein ethyoxyl method and the step alcoholysis method of phthalein chlorine two is strict to process specifications, and material toxicity is larger.This paper is using direct Esterification process prepares PEG fatty acid esters, is PEG aliphatic acid with polyalcohols high and aliphatic acid direct esterification under the catalysis of acid catalyst Ester, the process is simple of the method, the esterification yield of the product for obtaining is also higher.
The cithrol that can be enumerated, including but not limited to, polyethylene glycol stearate, ethylene glycol list are stearic Acid esters, EGDS, EGDS, EGDS, PEG400 monostearate The double stearates of ester, PEG400；Polyethylene glycol laurate, Cithrol 2ML, polyethylene glycol 200 are double Laurate, Cithrol 4ML, PEG400 bilaurate；Polyethylene glycol (PEG) oleate, polyethylene glycol 400 monoleates, PEG400 dioleic acid ester, Macrogol 600 monoleate, Macrogol 600 dioleic acid ester, poly- second The monoleate of glycol 4000, Macrogol 6000 monoleate, PEG-264 oleates.
In a preferred embodiment, the fatty alcohol ether, cithrol, styrylphenol polyoxy Weight ratio between vinethene is 1：10：10~100；Preferably, the fatty alcohol ether, cithrol, styrene Weight ratio between base phenol APEO is 1：10：30~70；Most preferably, the fatty alcohol ether, polyethylene glycol fatty acid Weight ratio between ester, styrylphenol polyoxyethylene ether is 1：10：89.
In a preferred embodiment, the also nanometer titanium dioxide including 0.1~0.5 weight portion is stated in terylene accelerant Silicon.
In a kind of preferred implementation method, the nano silicon is meso-porous nano silica.
In the present invention, the nano silicon for being used is commercially available acquisition.
The fourth aspect of the invention provides the preparation method of the terylene accelerant, at least comprises the following steps：
After above-mentioned each material is mixed, 50~80 DEG C are warming up to, are stirred 1~2 hour under 60~120r/min speed, after 30~40 DEG C are cooled to, discharging obtains terylene accelerant.
The suitable dyestuff of accelerant provided by the present invention includes acid dyes, azoic dyes, direct dyes, dispersion dye Material, reactive dye, sulfur dye, reducing dye.
Acid dyes includes strong acid type dye, weak acid dye, acidic complex dye, neutral dye, acid mordant dye.
The instantiation of highly acid dyestuff is included but is not limited to：Acid Light Yellow G, acid brilliant yellow 2g, Indian yellow E-GNL, acid Golden yellow, the Indian yellow R of property, Indian yellow GR, acid orange E-3R, Acid Orange II, acid orange G, acid scarlet 2G, acid orange AGT, acidity Red G, acid bright red E-B, Acid Red B, acid red R, acid red 6B, Acid Red B G, Acid Rose Red B, Acid Brilliant Scarlet GR, acidity It is red A, Acid violet 2R, acid violet red B, acid violet 4BNS, acid violet 5B, acid sky blue v, acid bright blue 2G, acid blue FG, water-soluble Indigo plant, Acid blue B RL, acid blue SE, Acid blue B, acid blue 2R, acid gorgeous blue 6B, acid gorgeous blue G, acid navy blue R, acid ink Water indigo plant G, acid bright green SF, acid green 6B, acid green VS, acid dark green B, acid green B S, acid brown K, acid brown DR, acid black 10B, acid particle element, acid black NT.The instantiation of weak acid dye is included but is not limited to：Weak acid yellow 3G, faintly acid are tender It is yellow 5G, weak acid yellow 6G, weak acid yellow P-L, weak acid yellow S, weak acid yellow 3GS, tracid light yellow 2G, Weakly Acid Bright Yellow G, weak Acid orange G S, weak acid orange PR, weak acid yellow RXL, weak acid orange N-RL, weak acid orange C-GNS, weak acid red E-BL, weak acid The bright red 3GL of property, weak acid red F-RS, weak acid red GN, Weak Acid Red 3B-E, the pink B of faintly acid, Weak Acid Red B L, weak acid It is the purplish red BB of property, Weak Acid Red 3B, Weak Acid Red B, weak acid red E-BM, faintly acid sauce red 5BL, the purplish red P-L of faintly acid, weak The bright red FG of rubrum scarlatinum FG, faintly acid, weak acid red GRS, weak acid red RN, weak acid red GN, faintly acid purple N-FBL, weak acid Property bright red 10B, the gorgeous blue A of faintly acid, acid anthraquinone blue, weak acid blue 2G, weak acid blue BRN, Weakly Acid Brilliant Blue RAW, faintly acid The gorgeous blue FFR of gorgeous blue 7BF, faintly acid, Weakly Acid Blue 5R, Weakly Acid Blue GR, the gorgeous blue GAW of faintly acid, the gorgeous blue P-R of faintly acid, The gorgeous blue 5GM of faintly acid, weak acid blue N-GL, weak acid blue BRLL, weak acid green GS, weak acid green 5GS, faintly acid bright green 6G, The reddish brown V of tracid brown R, faintly acid, the yellowish-brown 3GL of faintly acid, Weakly Acid Black BR, tracid black VL, tracid black BG, tracid black RB, tracid black NB-G.
The instantiation of acidic complex dye is included but is not limited to：Acidity complexing Huang GR, the acid black WAN of complexing.
The instantiation of neutral dye is included but is not limited to：Neutral dark yellow GRL, neutral gorgeous yellow 3GL, neutral dark yellow GL, in Property deep yellow 5GL, neutral orange RL, dimethyl diaminophenazine chloride 2GL, neutral bordeaux GRL, neutral pink BL, neutral violet BL, neutral blue BNL, neutral gorgeous Blue GL, neutral gorgeous blue M-5G, neutral bright green BL, neutral brown RL, neutral ash 2BL, neutral black BGL, neutral black BL, neutral black BRL, Neutral black 2S-RL, neutral black M-SRL.
The instantiation of acid mordant dye is included but is not limited to：The deep yellow CG of acidic intermedium, acid mordant orange R, acid matchmaker Be situated between orange G, acid mordant red S-80, Acid Chrome Bordeaux BN, acidic Mordant Red B, the pink 3BM of acidic intermedium, acidic intermedium drift indigo plant B, acid mordant blue A3R, acid mordant dark blue AGLO, the green G of acidic intermedium, Acid Mordant Brown RH, acid media black A, acid matchmaker Be situated between black PV, Mordant Black T, acid mordant grey BS, acid mordant black R, acid mordant grey GLN, acid mordant grey BN.
Azoic dyes include azoic coupling component, color base.
The instantiation of azoic coupling component is included but is not limited to：Azoic coupling component AS, azoic coupling component AS-BR, azoic coupling component AS-BO, azoic coupling component AS-SW, azoic coupling component AS-L4G, Naphthol AS-E, azoic coupling component AS-RL, azoic coupling component AS-ITR, azoic coupling component AS-SG, Naphthol AS-PH, azoic coupling component AS-BT, apthol AS, Naphthol AS-D, azoic coupling component AS-BG, Naphthol AS-OL, apthol AS-LC, azoic coupling component AS-LT, azoic coupling component AS-SR, azoic coupling component AS-RS, azoic coupling component AS- MX, azoic coupling component AS-VL, azoic coupling component AS-S, azoic coupling component AS-CA, apthol AS-IRG.
The instantiation of color base is included but is not limited to：It is chloroaniline GC, orange base GC, orange base GR, purplish red color base GP, bright red Color base GGS, purplish red color base GBC, Fast Red B base, red-base GL, red base 3GL, Fast Red RC base, large red-based g, erie Congo base RC, Red base SW, erie Congo base VD, erie Congo base LG, red base KB, red base FR, fast red rl, red base ITL, erie Congo base TR, red base KL, fast red KD base, red base K, Fast Blue BB base, Fast Blue VRT salt, Fast Blue VB salt, brown salt V, black salt K, black Salt G, fast black base G, fast black base B, fast black base LS.
Direct dyes includes general direct dyes, direct fast dye, direct blend dye.
The instantiation of general direct dyes is included but is not limited to：Direct light yellow 5G, direct yellow R, directly gorgeous yellow 4R, directly Orange S, directly direct bordeaux GB, red B, directly resistance to semen ziziphi spinosae red, direct pink, direct bordeaux NGB, direct sky blue 5B, direct mantoquita Blue BR, direct green B, direct dark green 2B-NB, direct dark green NB, direct green B N, directly dark brown NM, direct red brown RN, directly ash D, Direct black RN, directly black OB, directly direct mantoquita ash GRL, black ANBA.
The instantiation of direct fast dye is included but is not limited to：Direct fast light yellow 5GL, direct fast yellow 2R, directly Everbright fast yellow 5R, direct fast yellow GC, direct fast yellow G, direct fast yellow RS, direct fast yellow L-5R, direct fast yellow ARL, It is direct everbright fast orange TGL, direct Fast Orange GGL, direct fast pink BK, direct fast red 4BL, direct fast red F3B, directly resistance to Turn to red because of sun burn 4B, direct sun-proof bordeaux B L, the pake purpke RLL of direct sun-proof, direct fast blue B2RL, direct fast blue FRL, direct fast blue The gorgeous blue BL of L4G, direct fast blue 2RLL, direct light turquoise GL, direct sun-proof, direct fast blue FFRL, direct sun-proof are green BLL, the green 5GLL of direct sun-proof, direct fast brown 8RLL, Direct fast light black G, Direct fast light black G F, direct fast grey LBN, directly Sun-proof ash 2BL.
The instantiation of direct blend dye is included but is not limited to：Direct blending Huang D-RL, direct blending Huang D-3RNL, directly Meet blending carbuncle D-BL, direct blending bright red D-5BL, direct blending bright red D-10BL, direct blended carbuncle D-BLL, directly mixed Spin bright red D-GLN, direct blending indigo plant D-3GL, direct blending brown D-RS, the black D-HR of direct blending.
The instantiation of disperse dyes is included but is not limited to：Disperse yellow G, disperse yellow 5G, disperse yellow E-5R, dispersion lemon Huang, Disperse Yellow RGFL, disperse yellow M-FL, the gorgeous yellow SE-6GFL of dispersion, disperse yellow M-FL, the gorgeous yellow SE-6GFL of dispersion, disperse yellow SE- 2GL, disperse yellow E-3G, disperse yellow 3G, scattered fluorescent yellow II, disperse yellow C-6GL, disperse yellow HG, scattered fluorescent yellow 8GFF, dispersion Yellow SE-5R, disperse gorgeous yellow 6GSL, disperse yellow 5GLH, scattered fluorescent yellow H-8GFL, disperse yellow SE-5GL, disperse light yellow H4GL, point Dissipate Huang NR, disperse yellow P-3R, disperse yellow H3GL, disperse yellow S-3GL, disperse orange GR, disperse orange SE-B, disperse orange F-3R, dispersion Orange SE-3GL, disperse orange S-4RL, disperse orange SE-2FL, disperse orange HFFG, disperse orange S-6RL, disperse orange R-SF, disperse yellow brown 3GL, disperse yellow brown 2RCW, disperse orange S-RL, disperse orange SE-RFL, disperse orange HGL, disperse scarlet B, Disperse Red R LZ, disperse red Beautiful 3B, smoke red, disperse violet, dispersion bordeaux B, Disperse Red R, disperse red SE-R, dispersion bright red E-RLN, disperse scarlet S-3GFL, Disperse Red 3B, disperse scarlet S-GR, disperse scarlet S-FL, dispersed ruby SE-GFL, disperse red S-R, dispersed ruby SE-BBL, point Scattered pink R3L, disperse scarlet BRE, disperse red 2BL-S, disperse scarlet G-S, disperse red S-5BL, disperse red FRL, dispersion are purplish red H-G, disperse red H-2GL, dispersion fluorescence red 2GL, disperse red P-4G, disperse red F3BS, disperse pink S-FL, disperse red S-BGL, Dispersed ruby P-B, disperse violet 4BN, disperse violet RL, disperse violet H-FRL, disperse red GB, disperse violet S-3RL, disperse violet 3RL S, Dispersion purple P-R, disperse violet CW, the gorgeous purple 3RLS of dispersion, disperse blue FFR, disperse blue B, disperse blue GFL, disperse blue E-BR, dispersion Blue 2BLN, disperse bright blue H-GL, Disperse Blue BGL, disperse dark blue S-3BG, disperse blue E-FRS, disperse blue FG, disperse blue BBLS, Disperse blue SE-2R, disperse navy blue 5G, disperse blue S-3GL, disperse blue CR-E, disperse blue GBS, disperse blue BR, disperse brown 3R, point Dissipate yellowish-brown REL, disperse brown S-3R, disperse brown P-3G, the black GNN of dispersion diazonium.
Reactive dye include X-type reactive dye, K-type reactive dye, KN types reactive dye, M type reactive dye KE types activity Dyestuff.
The instantiation of X-type reactive dye is included but is not limited to：Reactive Light Yellow X-6G, active yellow X-R, reactive brilliant yellow X- 7G, active yellow X-RG, reactive brilliant yellow X-4G, active golden yellow X-G, reactive brilliant orange X-2R, the gorgeous yellow X-4R of activity, reactive brilliant orange X- 7R, Reactive Orange X-GN, reactive brilliant orange X-GR, reactive brilliant red X-B, reactive brilliant red x-3b, active carbuncle X-B, reactive brilliant red X-7B, Reactive brilliant red X-8B, reactive red violet X-2R, reactive blue X-3G, Reactive Brilliant Blue X-BR, reactive blue X-2R, reactive blue X-R.
The instantiation of K-type reactive dye is included but is not limited to：Reactive brilliant yellow K-6G, active yellow K-RN, reactive brilliant yellow K- 4G, reactive orange K-G, reactive brilliant orange k-gn, active golden yellow K-3RP, active golden yellow K-2RA, reactive brilliant orange K-7G, reactive brilliant orange K- 2GN, reactive brilliant orange K-R, reactive brilliant orange K-7R, active red K-3B, active red K-7B, reactive brilliant red k-2g, reactive brilliant red K- 2BP, reactive brilliant red K-G, active red KD-G, active purple k-3r, reactive violet K-2R, reactive blue K-3G, reactive brilliant bule K-GR, activity Dark blue K-R, reactive turquoise blue K-GL, reactive brilliant bule K-3R, reactive yellow brown K-GR, active reddish brown K-B2R, active ash K-B4RP, work The black K-BR of property.
The instantiation of KN type reactive dye is included but is not limited to：Reactive brilliant yellow KN-G, active golden yellow KN-G, reactive brilliant yellow KN-7G, reactive brilliant orange KN-4R, reactive orange KN-5R, reactive brilliant orange KN-2G, active red KN-5B, active red sauce KN-B, active red Purple KN-R, reactive violet KN-4R, active red-violet KN-2R, Reactive Brilliant Blue KN-R, Reactive Turquoise Blue KN-G, reactive brilliant bule KN-B, activity Black KN-B.
The instantiation of M type reactive dye is included but is not limited to：Active yellow M-3RE, reactive brilliant yellow M-5G, active yellow M- 5R, reactive brilliant yellow KM-7G, active red M-2BE, reactive brilliant red M-3BE, active red M-RBE, reactive brilliant red KM-2B, active red M- 3BE, reactive brilliant red KM-8B, active purplish red M-R, reactive dark blue KM-GR, reactive dark blue M-2GE, Reactive Turquoise Blue KM-GB, activity Gorgeous blue M-BR, reactive dark blue M-R, activity red engleri K-B 3 R, active yellowish-brown K-GN, active black M-2R.
The instantiation of KE type reactive dye is included but is not limited to：Reactive brilliant yellow KE-3G, reactive brilliant yellow KE-5G, active yellow KE-4G, active yellow KE-4RN, active yellow KE-RN, active yellow KE-3G, reactive orange KE-G, reactive orange KE-2G, reactive brilliant orange KE- 2R, active red KE-3B, reactive brilliant red KE-7B, reactive scarlet KE-3G, active red KD-8B, reactive dark blue KE-R, active green KE- 4B。
The instantiation of sulfur dye is included but is not limited to：Sulphur Yellow GC, sulphur light yellow G, sulfur yellow brown 6g, sulphur red brown B3R, sulphur dark-blue 3R, SULPHAR DYES BLUE BRN, vulcanization Xinlan BBF, sulfur blue CV, reversion indigo plant B, Sulphur Indanthrene Blue RNX, vulcanization Vat blue GNX, sulphur brilliant green G B, sulphur bright green, sulphur grass-green, sulphur dark-green, sulphur vat nile green G, the dark brown GN of vulcanization, vulcanization Yellowish-brown 5G, sulphur black BN, the black CLG of reversion.
The instantiation of reducing dye is included but is not limited to：Reducing yellow G, Vat Yellow GCN, reducing yellow G K, Vat Yellow2 GF, Vat yellow 3GFN, vat yellow 4GF, vat yellow 6GD, Vat YellowF3 GC, Vat Golden Yellow RK, Vat Brilliant Orange 3RK, reductive bright orange GR, Vat golden orange G, vat yellow 3RT, Vat Orange 3 G, vat orange G, pink vat dye R, Threne brilliant pink S-3B, vat red FBB, vat red 6B, vat scarlet GG, vat bordeaux 2R, vat red 2G, vat scarlet R, vat red F3B, reduction bright red LGG, vat red 5GK, Vat scarlet G, Threne brilliant pink 3B, vat brilliant violet RR, soluble vat violet I4R, reduction purple RRN, reduction purple RRK, reduction Gorgeous purple RK, indigotin, Vat Blue RSN, Bromo-Indigo, Vat Blue BC, the gorgeous blue 3G of reduction, vat blue GCDN, reduction are dark blue RA, Vat Dark Blue BO, the gorgeous blue 4G of reduction, vat blue ER, Vat Brilliant Green FFB, vat brilliant green 2G, Vat Olive Green B, reduction khaki 2G, Vat Black BBN, vat green BB, vat olive 3G, Vat Brown BR, vat brown R, vat brown B, vat brown 5R, vat red brown 5RF, vat brown G, vat brown GG, vat brown 3GR, Vat Grey M, vat direct black RB, vat direct black SNA, reduced olive T, Vat Olive R, Vat Grey BG.
The present inventor is found surprisingly that, by gaultherolin or gaultherolin derivative by being obtained after etherification reaction Etherification reaction product, after being applied to accelerant, dyeing accelerant, can cause that accelerant has extraordinary dye-uptake and wet-milling The reason for wiping the properties such as color fastness, conjecture possibility is that the gaultherolin after etherificate can strengthen polyster fibre and dye The interaction of material, and then play beneficial effects of the present invention.Additionally, spreading out by the gaultherolin or gaultherolin that are etherified Biological almost no any smell, through hyperchromatic fabric also without any peculiar smell, solving existing accelerant has stimulation The problem of property smell.
The fifth aspect of the invention provides etherificate gaultherolin in textile printing and dyeing, plasticizer, flavouring agent field Using.
The present invention is specifically described below by embodiment.Be necessary it is pointed out here that, following examples are only used In the invention will be further described, it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field Some nonessential modifications and adaptations that content according to the invention described above is made, still fall within protection scope of the present invention.
In addition, if without other explanations, raw materials used is all commercially available, and number used by following material is weight Part.
Embodiment 1：
Embodiments of the invention 1 provide a kind of terylene accelerant, the terylene accelerant, in parts by weight, including：
100 parts of nonionic surfactant；
1 part of gaultherolin of etherificate；
The nonionic surfactant is：Polyoxyethylene stearyl base ether, PEG400 double stearate, triphen second Alkenyl benzene phenol polyethenoxy ether is 1 according to weight portion：10：89 mixing nonionic surfactant.
The etherificate gaultherolin is to include that gaultherolin and etherifying reagent expoxy propane are obtained by etherification reaction.
The preparation method of the etherificate gaultherolin is comprised the following steps：
Gaultherolin, expoxy propane are dissolved in dimethyl sulfoxide (DMSO) as reaction system, wherein, gaultherolin, ring Ethylene Oxide, the mol ratio of dimethyl sulfoxide (DMSO) are 1：1：40.The dilute sulfuric acid that mass fraction is 1% is added, wherein, the weight of dilute sulfuric acid It is the 30% of gaultherolin to measure, and by reaction system at 60 DEG C, reacts 7h, obtains being etherified gaultherolin.
The preparation method of the terylene accelerant is：
After above-mentioned each material is mixed, be warming up to 50 DEG C, stirred 2 hours under 120r/min speed, after be cooled to 30 DEG C, Discharging, obtains terylene accelerant.
Embodiment 2：
Embodiments of the invention 2 provide a kind of terylene accelerant, the terylene accelerant, in parts by weight, including：
100 parts of nonionic surfactant；
8 parts of gaultherolin of etherificate；
The nonionic surfactant is：Polyoxyethylene stearyl base ether, PEG400 double stearate, triphen second Alkenyl benzene phenol polyethenoxy ether is 1 according to weight portion：10：89 mixing nonionic surfactant.
The etherificate gaultherolin is to include that gaultherolin and etherifying reagent expoxy propane are obtained by etherification reaction.
The preparation method of the etherificate gaultherolin is comprised the following steps：
Gaultherolin, expoxy propane are dissolved in dimethyl sulfoxide (DMSO) as reaction system, wherein, gaultherolin, ring Ethylene Oxide, the mol ratio of dimethyl sulfoxide (DMSO) are 1：1：40.The dilute sulfuric acid that mass fraction is 1% is added, wherein, the weight of dilute sulfuric acid It is the 30% of gaultherolin to measure, and by reaction system at 60 DEG C, reacts 7h, obtains being etherified gaultherolin.
The preparation method of the terylene accelerant is：
After above-mentioned each material is mixed, be warming up to 50 DEG C, stirred 2 hours under 120r/min speed, after be cooled to 30 DEG C, Discharging, obtains terylene accelerant.
Embodiment 3：
Embodiments of the invention 3 provide a kind of terylene accelerant, the terylene accelerant, in parts by weight, including：
100 parts of nonionic surfactant；
3 parts of gaultherolin of etherificate；
The nonionic surfactant is：Polyoxyethylene stearyl base ether, PEG400 double stearate, triphen second Alkenyl benzene phenol polyethenoxy ether is 1 according to weight portion：10：89 mixing nonionic surfactant.
The etherificate gaultherolin is to include that gaultherolin and etherifying reagent expoxy propane are obtained by etherification reaction.
The preparation method of the etherificate gaultherolin is comprised the following steps：
Gaultherolin, expoxy propane are dissolved in dimethyl sulfoxide (DMSO) as reaction system, wherein, gaultherolin, ring Ethylene Oxide, the mol ratio of dimethyl sulfoxide (DMSO) are 1：1：40.The dilute sulfuric acid that mass fraction is 1% is added, wherein, the weight of dilute sulfuric acid It is the 30% of gaultherolin to measure, and by reaction system at 60 DEG C, reacts 7h, obtains being etherified gaultherolin.
The preparation method of the terylene accelerant is：
After above-mentioned each material is mixed, be warming up to 50 DEG C, stirred 2 hours under 120r/min speed, after be cooled to 30 DEG C, Discharging, obtains terylene accelerant.
Embodiment 4：
Embodiments of the invention 4 provide a kind of terylene accelerant, the terylene accelerant, in parts by weight, including：
100 parts of nonionic surfactant；
3 parts of gaultherolin of etherificate；
The nonionic surfactant is：Polyoxyethylene stearyl base ether, PEG400 double stearate, triphen second Alkenyl benzene phenol polyethenoxy ether is 1 according to weight portion：10：89 mixing nonionic surfactant.
The etherificate gaultherolin is to include that gaultherolin and etherifying reagent oxirane are obtained by etherification reaction.
The preparation method of the etherificate gaultherolin is comprised the following steps：
Gaultherolin, oxirane are dissolved in absolute ethyl alcohol as reaction system, wherein, gaultherolin, epoxy Ethane, the mol ratio of absolute ethyl alcohol are 1：1：50.The dilute sulfuric acid that mass fraction is 1% is added, wherein, the weight of dilute sulfuric acid is The 20% of gaultherolin, by reaction system at 100 DEG C, reacts 7h, obtains being etherified gaultherolin.
The preparation method of the terylene accelerant is：
After above-mentioned each material is mixed, be warming up to 80 DEG C, stirred 2 hours under 70r/min speed, after be cooled to 30 DEG C, Discharging, obtains terylene accelerant.
Embodiment 5：
Embodiments of the invention 5 provide a kind of terylene accelerant, the terylene accelerant, in parts by weight, including：
100 parts of nonionic surfactant；
3 parts of gaultherolin of etherificate；
The nonionic surfactant is：Polyoxyethylene stearyl base ether, PEG400 double stearate, triphen second Alkenyl benzene phenol polyethenoxy ether is 1 according to weight portion：10：89 mixing nonionic surfactant.
The etherificate gaultherolin is to include that gaultherolin and etherifying reagent polyethylene glycol are obtained by etherification reaction.
The preparation method of the etherificate gaultherolin is comprised the following steps：
Gaultherolin, polyethylene glycol are dissolved in absolute ethyl alcohol as reaction system, wherein, gaultherolin, poly- second Glycol, the mol ratio of absolute ethyl alcohol are 1：1：50.The dilute sulfuric acid that mass fraction is 1% is added, wherein, the weight of dilute sulfuric acid is The 20% of gaultherolin, by reaction system at 100 DEG C, reacts 7h, obtains being etherified gaultherolin.
The preparation method of the terylene accelerant is：
After above-mentioned each material is mixed, be warming up to 70 DEG C, stirred 2 hours under 100r/min speed, after be cooled to 30 DEG C, Discharging, obtains terylene accelerant.
Embodiment 6：
Embodiments of the invention 6 provide a kind of terylene accelerant, the terylene accelerant, in parts by weight, including：
100 parts of nonionic surfactant；
3 parts of gaultherolin of etherificate；
The nonionic surfactant is：Polyoxyethylene stearyl base ether, PEG400 double stearate, triphen second Alkenyl benzene phenol polyethenoxy ether is 1 according to weight portion：10：89 mixing nonionic surfactant.
The etherificate gaultherolin is to include that gaultherolin and etherifying reagent polyethylene glycol are obtained by etherification reaction.
The preparation method of the etherificate gaultherolin is comprised the following steps：
Gaultherolin, polyethylene glycol are dissolved in absolute ethyl alcohol as reaction system, wherein, gaultherolin, poly- second Glycol, the mol ratio of absolute ethyl alcohol are 1：1：50.The dilute sulfuric acid that mass fraction is 1% is added, wherein, the weight of dilute sulfuric acid is The 20% of gaultherolin, by reaction system at 100 DEG C, reacts 7h, obtains being etherified gaultherolin.
The preparation method of the terylene accelerant is：
After above-mentioned each material is mixed, be warming up to 70 DEG C, stirred 2 hours under 100r/min speed, after be cooled to 30 DEG C, Discharging, obtains terylene accelerant.
Embodiment 7：
Embodiments of the invention 7 provide a kind of terylene accelerant, the terylene accelerant, in parts by weight, including：
100 parts of nonionic surfactant；
3 parts of gaultherolin of etherificate；
The nonionic surfactant is：Polyoxyethylene stearyl base ether, PEG400 double stearate, triphen second Alkenyl benzene phenol polyethenoxy ether is 1 according to weight portion：10：89 mixing nonionic surfactant.
The etherificate gaultherolin is to include that gaultherolin and etherifying reagent propane diols are obtained by etherification reaction.
The preparation method of the etherificate gaultherolin is comprised the following steps：
Gaultherolin, propane diols are dissolved in dimethyl sulfoxide (DMSO) as reaction system, wherein, gaultherolin, the third two Alcohol, the mol ratio of dimethyl sulfoxide (DMSO) are 1：1：30.The dilute sulfuric acid that mass fraction is 1% is added, wherein, the weight of dilute sulfuric acid is The 20% of gaultherolin, by reaction system at 100 DEG C, reacts 7h, obtains being etherified gaultherolin.
The preparation method of the terylene accelerant is：
After above-mentioned each material is mixed, be warming up to 70 DEG C, stirred 2 hours under 100r/min speed, after be cooled to 30 DEG C, Discharging, obtains terylene accelerant.
Embodiment 8：
Embodiments of the invention 8 provide a kind of terylene accelerant, the terylene accelerant, in parts by weight, including：
100 parts of nonionic surfactant；
3 parts of gaultherolin of etherificate；
The nonionic surfactant is：Polyoxyethylene stearyl base ether, PEG400 double stearate, triphen second Alkenyl benzene phenol polyethenoxy ether is 1 according to weight portion：10：89 mixing nonionic surfactant.
The etherificate gaultherolin is to include that gaultherolin and etherifying reagent cyclodextrin are obtained by etherification reaction.
The preparation method of the etherificate gaultherolin is comprised the following steps：
Gaultherolin, cyclodextrin are dissolved in dimethyl sulfoxide (DMSO) as reaction system, wherein, gaultherolin, ring paste Essence, the mol ratio of dimethyl sulfoxide (DMSO) are 1：1：30.The dilute sulfuric acid that mass fraction is 1% is added, wherein, the weight of dilute sulfuric acid is The 20% of gaultherolin, by reaction system at 100 DEG C, reacts 7h, obtains being etherified gaultherolin.
The preparation method of the terylene accelerant is：
After above-mentioned each material is mixed, be warming up to 70 DEG C, stirred 2 hours under 100r/min speed, after be cooled to 30 DEG C, Discharging, obtains terylene accelerant.
Embodiment 9：
Embodiments of the invention 9 provide a kind of terylene accelerant, the terylene accelerant, in parts by weight, including：
100 parts of nonionic surfactant；
3 parts of gaultherolin of etherificate；
The nonionic surfactant is：Polyoxyethylene stearyl base ether, PEG400 double stearate, triphen second Alkenyl benzene phenol polyethenoxy ether is 1 according to weight portion：10：89 mixing nonionic surfactant.
The etherificate gaultherolin is to include that gaultherolin and the hydroxy-end capped super branched polyurethane of etherifying reagent pass through Etherification reaction is obtained.
The preparation method of the etherificate gaultherolin is comprised the following steps：
Gaultherolin, hydroxy-end capped super branched polyurethane are dissolved in dimethyl sulfoxide (DMSO) as reaction system, wherein, water Poplar acid methyl esters, hydroxy-end capped super branched polyurethane, the mol ratio of dimethyl sulfoxide (DMSO) are 1：1：30.It is 1% to add mass fraction Dilute sulfuric acid, wherein, the weight of dilute sulfuric acid is the 20% of gaultherolin, by reaction system at 100 DEG C, reacts 7h, is obtained Etherificate gaultherolin.
The preparation method specific steps of hydroxy-end capped super branched polyurethane：3 grams of pentaerythrites (PER) are taken with 20 grams of N, N- bis- NMF (DMF) dissolves, and obtains terminal hydroxy group small molecule polyol solution.By 11.67 grams of IPDIs (IPDI) 90 DEG C are heated to, terminal hydroxy group small molecule polyol solution stirring reaction is added 6 hours, the hyperbranched pre-polymerization of the first generation is obtained Thing a1.By 34.67 grams of first generation hyper-branched prepolymers a110 DEG C are cooled to 20 grams of diethanol amine, blending reaction 6 hours are incubated, Products therefrom is vacuum dried with after water separating-purifying, obtains hydroxy-end capped super branched polyurethane.
The preparation method of the terylene accelerant is：
After above-mentioned each material is mixed, be warming up to 70 DEG C, stirred 2 hours under 100r/min speed, after be cooled to 30 DEG C, Discharging, obtains terylene accelerant.
Embodiment 10：
Embodiments of the invention 10 provide a kind of terylene accelerant, the terylene accelerant, in parts by weight, including：
100 parts of nonionic surfactant；
3 parts of gaultherolin of etherificate；
0.1 part of nano silicon；
The nonionic surfactant is：Polyoxyethylene stearyl base ether, PEG400 double stearate, triphen second Alkenyl benzene phenol polyethenoxy ether is 1 according to weight portion：10：89 mixing nonionic surfactant.
The etherificate gaultherolin is with embodiment 9.
The nano silicon is purchased from Nanjing Tian Hang new materials Co., Ltd, and product type is TSP-L15.
The preparation method of the terylene accelerant is：
After above-mentioned each material is mixed, be warming up to 70 DEG C, stirred 2 hours under 100r/min speed, after be cooled to 30 DEG C, Discharging, obtains terylene accelerant.
Embodiment 11：
Embodiments of the invention 11 provide a kind of terylene accelerant, the terylene accelerant, in parts by weight, including：
100 parts of nonionic surfactant；
3 parts of gaultherolin of etherificate；
0.1 part of nano silicon；
The nonionic surfactant is：Polyoxyethylene stearyl base ether, PEG400 double stearate, triphen second Alkenyl benzene phenol polyethenoxy ether is 1 according to weight portion：10：89 mixing nonionic surfactant.
The etherificate gaultherolin is with embodiment 9.
The nano silicon is meso-porous nano silica, and name of product is：SBA-15, is purchased from Nanjing Ji Cang nanometers Science and Technology Ltd..
The preparation method of the terylene accelerant is：
After above-mentioned each material is mixed, be warming up to 70 DEG C, stirred 2 hours under 100r/min speed, after be cooled to 30 DEG C, Discharging, obtains terylene accelerant.
Comparative example 1：
Comparative example of the invention 1 provide a kind of terylene accelerant, the terylene accelerant, in parts by weight, including：
100 parts of nonionic surfactant；
3 parts of gaultherolin；
The nonionic surfactant is：Polyoxyethylene stearyl base ether, PEG400 double stearate, triphen second Alkenyl benzene phenol polyethenoxy ether is 1 according to weight portion：10：89 mixing nonionic surfactant.
The preparation method of the terylene accelerant is：
After above-mentioned each material is mixed, be warming up to 50 DEG C, stirred 2 hours under 120r/min speed, after be cooled to 30 DEG C, Discharging, obtains terylene accelerant.
Comparative example 2：
Comparative example of the invention 2 provide a kind of terylene accelerant, the terylene accelerant, in parts by weight, including：
100 parts of nonionic surfactant；
3 parts of gaultherolin；
The nonionic surfactant is only polyoxyethylene stearyl base ether；
The preparation method of the terylene accelerant is：
After above-mentioned each material is mixed, be warming up to 50 DEG C, stirred 2 hours under 120r/min speed, after be cooled to 30 DEG C, Discharging, obtains terylene accelerant.
Comparative example 3：
Comparative example of the invention 3 provide a kind of terylene accelerant, the terylene accelerant, in parts by weight, including：
100 parts of nonionic surfactant；
3 parts of gaultherolin；
The nonionic surfactant is only the double stearates of PEG400；
The preparation method of the terylene accelerant is：
After above-mentioned each material is mixed, be warming up to 50 DEG C, stirred 2 hours under 120r/min speed, after be cooled to 30 DEG C, Discharging, obtains terylene accelerant.
Comparative example 4：
Comparative example of the invention 4 provide a kind of terylene accelerant, the terylene accelerant, in parts by weight, including：
100 parts of nonionic surfactant；
3 parts of gaultherolin；
The nonionic surfactant is only tristyrylphenol polyoxyethylene ether；
The preparation method of the terylene accelerant is：
After above-mentioned each material is mixed, be warming up to 50 DEG C, stirred 2 hours under 120r/min speed, after be cooled to 30 DEG C, Discharging, obtains terylene accelerant.
Evaluation method
Dyeing：
By embodiment and the product of comparative example, it is 1 to be added to bath raio:In 20 treatment fluid, wherein, terylene accelerant Concentration is 0.1g/L；Dacron is put into Disperse Blue 2BLN respectively, 120 DEG C are warming up to the speed of 2 DEG C/min, kept 30min；40 DEG C are cooled to, washing drying is tested standby.
1st, dye-uptake is determined
In dyeing course, the ratio between upper dye to the amount of dye on dacron and dyestuff total amount in initial dye bath.
2nd, homogenized diet test
Bioassay standard uses GB/T 6687-2006.Level-dyeing property is divided into 5 grades, and 1 grade worst.5 grades best.Evaluation method is handle The dye sample of the dyeing for putting into afterwards compares with five grades of normal gradients, and its color depth is suitable with which gradient, then dyeability is set to several Level.
3rd, colour fastness to rubbing
By GB/T 3920-2008《Textile color stability tests colour fastness to rubbing》Determine, be divided into and determine twice, the Once after wet friction 50, to be tested, second to be tested after wet friction 200 times, 5 grades of test result point, 5 grades for most Good, 1 grade is worst.
4th, WASHING COLOR FASTNESS
WASHING COLOR FASTNESS, bioassay standard uses GB/T 3921-2008.
Fade or the degree of staining should be tested in the case where light source is specified, graded with standard gray card, as a result divide 5 grades, 5 grades for most Good, 1 grade is worst.
The characterization test of table 1
As can be seen that accelerant of the invention has upper dye very high from embodiments of the invention and comparative example Rate, level-dyeing property, wet friction color fastness, WASHING COLOR FASTNESS.Especially there is extraordinary moisture-proof colorfastness to rubbing.Additionally, this hair Bright accelerant almost without any penetrating odor, does not have any peculiar smell through hyperchromatic fabric, solves existing rush dye Agent has the problem of penetrating odor.Can more accord with the demands of the market, be a kind of new accelerant that can be widelyd popularize.
Foregoing example is merely illustrative, some features of the feature for explaining the disclosure.Appended claim The scope as wide as possible for requiring to be contemplated that is intended to, and embodiments as presented herein is only according to all possible embodiment Combination selection implementation method explanation.Therefore, the purpose of applicant is appended claim not by the explanation present invention Feature example selectional restriction.And the progress in science and technology by formed language performance it is inaccurate due to and not The possible equivalent or son being presently considered are replaced, and these changes should also be interpreted by appended in the conceived case Claim is covered.

Claims (10)

1. it is a kind of to be etherified gaultherolin, it is characterised in that the etherificate gaultherolin at least includes gaultherolin or water Poplar acid methyl ester derivation, etherifying reagent are obtained by etherification reaction；
The etherifying reagent is selected from any one in epoxies etherifying reagent or alcohols etherifying reagent.
2. it is as claimed in claim 1 to be etherified gaultherolin, it is characterised in that the epoxies etherifying reagent is selected from：Epoxy Ethane, expoxy propane, epoxy butane, 1,2- cyclopentane epoxides, oxepane, 1,2- oxepanes, 2- octylene oxides, the epoxy last of the ten Heavenly stems Any one or a few combination in alkane.
3. it is as claimed in claim 1 to be etherified gaultherolin, it is characterised in that the alcohols etherifying reagent is selected from：Ethylene glycol, Diethylene glycol, propane diols, butanediol, pentanediol, ethylene glycol, glycerine, polyvinyl alcohol, polyethylene glycol, cyclodextrin, shitosan, Any one or a few combination in hydroxy-end capped super branched polyurethane.
4. as described in claims 1 to 3 etherificate gaultherolin preparation method, it is characterised in that at least including following step Suddenly：
Gaultherolin or gaultherolin derivative, etherifying reagent are dissolved in organic solvent as reaction system, matter is added Amount fraction is 1% dilute sulfuric acid, wherein, the weight of dilute sulfuric acid for gaultherolin or gaultherolin derivative 30%~ 60%, by reaction system at 50~100 DEG C, 3~7h is reacted, obtain being etherified gaultherolin.
5. the preparation method of gaultherolin is etherified as claimed in claim 4, it is characterised in that the gaultherolin or water Poplar acid methyl ester derivation is 1 with the mol ratio of etherifying reagent：1~3.
6. a kind of terylene accelerant, it is characterised in that the terylene accelerant, in parts by weight, at least includes：
100 parts of nonionic surfactant；
1~8 part of etherificate gaultherolin described in claims 1 to 3；
Wherein, the nonionic surfactant at least includes that fatty alcohol ether, cithrol, styrylphenol gather Oxygen vinethene.
7. terylene accelerant as claimed in claim 6, it is characterised in that the fatty alcohol ether, cithrol, benzene Weight ratio between vinyl benzene phenol polyethenoxy ether is 1：10：10~100.
8. terylene accelerant as claimed in claim 6, it is characterised in that also include 0.1~0.5 weight in the terylene accelerant Measure the nano silicon of part.
9. the preparation method of terylene accelerant as claimed in claim 6, it is characterised in that at least comprise the following steps：
After material is mixed, be warming up to 50~80 DEG C, stirred 1~2 hour under 60~120r/min speed, after be cooled to 30~ 40 DEG C, discharging obtains terylene accelerant.
10. as described in claims 1 to 3 etherificate gaultherolin textile printing and dyeing, plasticizer, flavouring agent field application.
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CN106866410A (en) * 2016-12-28 2017-06-20 北京化工大学 A kind of PVC plasticizer and preparation method thereof
CN111809417A (en) * 2020-07-15 2020-10-23 浙江省现代纺织工业研究院 Nano dyeing promoter
CN115612435A (en) * 2022-10-20 2023-01-17 唯万科技有限公司 High-temperature-resistant polyurethane adhesive for sealing and preparation method thereof

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* Cited by examiner, † Cited by third party
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CN106866410A (en) * 2016-12-28 2017-06-20 北京化工大学 A kind of PVC plasticizer and preparation method thereof
CN106866410B (en) * 2016-12-28 2019-11-15 北京化工大学 A kind of PVC plasticizer and preparation method thereof
CN111809417A (en) * 2020-07-15 2020-10-23 浙江省现代纺织工业研究院 Nano dyeing promoter
CN111809417B (en) * 2020-07-15 2022-10-25 浙江省现代纺织工业研究院 Nano dyeing promoter
CN115612435A (en) * 2022-10-20 2023-01-17 唯万科技有限公司 High-temperature-resistant polyurethane adhesive for sealing and preparation method thereof
CN115612435B (en) * 2022-10-20 2023-09-12 唯万科技有限公司 High-temperature-resistant polyurethane adhesive for sealing and preparation method thereof

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