CN1333792A - Terephthalate-based sulfopolyesters - Google Patents
Terephthalate-based sulfopolyesters Download PDFInfo
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- CN1333792A CN1333792A CN 99815831 CN99815831A CN1333792A CN 1333792 A CN1333792 A CN 1333792A CN 99815831 CN99815831 CN 99815831 CN 99815831 A CN99815831 A CN 99815831A CN 1333792 A CN1333792 A CN 1333792A
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- acid
- sulfopolyester
- glycol
- derivatives
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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
- D06M15/5075—Polyesters containing sulfonic groups
-
- 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
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
-
- 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
- D06M7/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made of other substances with subsequent freeing of the treated goods from the treating medium, e.g. swelling, e.g. polyolefins
-
- 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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/35—Abrasion, pilling or fibrillation resistance
-
- 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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
This invention relates to water-dispersible sulfopolyesters comprising residues of (i) terephthalic acid; (ii) an amount sufficient to provide water-dispersibility to the sulfopolyester of at least one difunctional sulfomonomer containing at least one sulfonate group bonded to an aromatic ring; (iii) less than 5 mole % of at least one dicarboxylic acid that is not terephthalic acid or a sulfomonomer; (iv) 25 to 90 mole % of at least one polyethylene glycol having the structure: H-(OCH2CH2)n-OH wherein 2 </=n < 20 with the proviso that the mole % of the polyethylene glycol is inversely proportional to the quantity n within the range; and (v) from greater than 10 to less than 75 mole % of hydroxyl equivalents of a glycol or mixture of glycols that is(are) not a polyethylene glycol. The water-dispersible sulfopolyesters according to the invention exhibit improved abrasion and blocking resistance when used as sizing compositions. Accordingly, in another embodiment the invention relates to a fibrous article sized with a sizing composition comprising a water-dispersible sulfopolyester as described above and method of making same.
Description
The U.S. Provisional Application sequence number 60/110808 of pending trial was as priority application when the application's requirement proposed with on December 3rd, 1998, and its disclosure is hereby incorporated by.
Invention field
The present invention relates to water dispersible sulfopolyester based on terephthalate units.Sulfopolyester of the present invention has easily disperse and excellent dispersion package stability, and is used as the wear resistance with improvement and the textile fibres slurry of resistance to blocking.
Background of invention
Fusion the water dispersible sulfopolyester of terephthalic acid and polyoxyethylene glycol unit be well known in the art.For example, United States Patent(USP) Nos. 3546008,3734874 and 3779993 has been lectured such sulfopolyester.These patents are pointed out, in order to obtain to have the sulfopolyester of abundant dispersiveness, when terephthalic acid is used as the dicarboxylic acid component, should use other acid of 5mol% at least.U.S. Patent No. 5290631 discloses the water dispersible sulfopolyester based on the repeated structural unit of terephthalate, isophthalic acid ester, sulfomonomer, ethylene glycol and polyoxyethylene glycol.Not open about based on the sulfopolyester that contains less than the acid constituents of the acid except that terephthalic acid or sulfomonomer of 5mol%.In fact, the sulfopolyester of this patent disclosure comprises 10 to 75mol% terephthalic acid units and 15 to 70mol% the unitary combination of m-phthalic acid.
The sulfopolyester composition that is scattered in only in water/alcohol mixture is disclosed in U.S. Patent No. 4525524.This sulfopolyester comprises the repeating unit from the dibasic acid component that contains 20 to 90mol% dimethyl terephthalate (DMT) or terephthalic acid.Diol component can comprise the two pure and mild glycol ethers that contain 4 to 12 carbon atoms that maximum 80mol% (based on total glycol) contain 3 to 12 carbon atoms.These components in water all are separately can not dispersive.
Be known in the art, when diol component contains high molecular weight polyethylene glycol, can increase the dispersiveness of sulfopolyester.For example, water dispersible sulfopolyester based on high molecular weight polyethylene glycol is disclosed in U.S. Patent No. 4233196.The molecular weight of polyoxyethylene glycol be 106 to 22018g/mol and total diol component comprise the polyoxyethylene glycol that is less than 15mol%.The same with above-mentioned patent, if this patent discloses the di-carboxylic acid component that terephthalic acid is used as polyester, just have only when using other acid of 5mol% at least, could obtain the result of requirement.In addition, the polyester that the molecular weight of increase polyoxyethylene glycol causes having the low glass state invert point, it causes the adhesion of starching particulate again.
Therefore, still need be based on the wear resistance of the easy water dispersible of having of terephthalic acid units, improvement and the water dispersible sulfopolyester of resistance to blocking.The present invention meets this requirement.
Summary of the invention
Have been found that, when acid constituents comprises terephthalate, the sulfomonomer that exists with sour form and contain 25mol% at least and during less than the polyoxyethylene glycol of at least a following formula of 90mol% less than other acid of 5mol% and diol component, can obtain basically water dispersible sulfopolyester based on the water dispersible with improvement, wear resistance and the resistance to blocking of terephthalate units
H-(OCH
2CH
2)
n-OH is 2≤n＜20 wherein.
Therefore, the present invention relates to the water dispersible sulfopolyester, it comprises:
(i) terephthalic acid or its derivative,
(ii) less than at least a dicarboxylic acid except terephthalic acid or derivatives thereof or sulfomonomer of about 5mol% (based on the total mole number of acid),
At least a polyoxyethylene glycol of (iii) about 25 to about 90mol% (based on total molecular fractions of hydroxyl equivalent) with following structural formula:
H-(OCH
2CH
2)
n-OH wherein the molecular fraction and the n value of 2≤n＜20 and the polyoxyethylene glycol that exists is inversely proportional to,
(iv) greater than about 10 to less than about 75mol% (based on total molecular fraction of hydroxyl equivalent) except polyoxyethylene glycol glycol or diol mixture and
(v) content is enough to provide at least a difunctional sulfomonomer of sulfopolyester water dispersible.
Sulfopolyester contains the acid equivalent (about 100mol%) and the hydroxyl equivalent (about 100mol%) of first-class substantially molar ratio, and therefore, the summation of acid and hydroxyl equivalent equals about 200mol%.Under the concentration of about 0.25g polymkeric substance in the 100ml solvent, 25 ℃, the limiting viscosity of the sulfopolyester of measuring in the phenol/tetrachloroethane solution of 60/40 part (weight) of the present invention is 0.1dL/g at least.
For providing the difunctional sulfomonomer of water dispersible, water dispersible sulfopolyester of the present invention is selected from: contain at least one dicarboxylic acid or derivatives thereof that is combined in the sulfonation group on the aromatic ring, contain at least one and be combined in two of sulfonation group on the aromatic ring and pure and mildly contain the alcohol acid or derivatives thereof that at least one is combined in the sulfonation group on the aromatic ring.
When water dispersible sulfopolyester of the present invention is used as paste compound, demonstrate the wear resistance and the resistance to blocking of improvement.Therefore, in another embodiment, the present invention relates to fibre product with the paste compound starching that contains above-mentioned water dispersible sulfopolyester.Detailed Description Of The Invention
The present invention relates to basically water dispersible sulfopolyester based on the water dispersible with improvement, wear resistance and the resistance to blocking of terephthalate units.Such sulfopolyester comprises the sulfomonomer that contains terephthalate, exist with sour form, less than other sour acid constituents and the diol component of 5mol%, wherein diol component contains 25mol% at least and less than the polyoxyethylene glycol of at least a following formula of 90mol%:
H-(OCH
2CH
2)
n-OH is 2≤n＜20 wherein.
Term " water dispersible " usually and other descriptor be used interchangeably, as " water-dispersion ", " water-soluble " and " loosing property of water drive ".In literary composition of the present invention, all these terms all are meant the activity of water to sulfopolyester described herein.Wish that this term comprises that the sulfopolyester dissolving forms pure solution or it disperses to obtain the condition of stable product in water medium.Usually, because the statistical of polymer blend, when acting on single sulfopolyester with water medium, it can contain solubilized and can disperse part.
As mentioned above, the present invention relates to the water dispersible sulfopolyester, it comprises:
(i) terephthalic acid or its derivative,
(ii) less than at least a dicarboxylic acid except terephthalic acid or derivatives thereof or sulfomonomer of about 5mol% (based on the total mole number of acid),
At least a polyoxyethylene glycol that contains following structure of (iii) about 25 to about 90mol% (based on total molecular fractions of hydroxyl equivalent):
H-(OCH
2CH
2) n-OH wherein the molecular fraction and the n value of 2≤n＜20 and the polyoxyethylene glycol that exists be inversely proportional to,
(iv) greater than about 10 to less than the glycol except polyoxyethylene glycol of about 75mol% (based on total molecular fraction of hydroxyl equivalent) or diol mixture and
(v) content is enough to provide at least a difunctional sulfomonomer of sulfopolyester water dispersible.
Sulfopolyester contains the acid equivalent (about 100mol%) and the hydroxyl equivalent (about 100mol%) of first-class substantially molar ratio, and therefore, the summation of acid and hydroxyl equivalent equals about 200mol%.Under the concentration of about 0.25g polymkeric substance in the 100ml solvent, 25 ℃, the limiting viscosity of the sulfopolyester of measuring in the phenol/tetrachloroethane solution of 60/40 part (weight) of the present invention is 0.1dL/g at least.Preferably, limiting viscosity is 0.25dL/g, more preferably 0.3dL/g at least.In order to improve adhesivity, the glass transition temperature of water dispersible sulfopolyester of the present invention is preferably at least 25 ℃, more preferably 25 to 75 ℃ and most preferably 30 to 65 ℃.
As mentioned above, water dispersible sulfopolyester of the present invention contains the terephthalic acid as acid constituents, and wherein the 95mol% at least of acid constituents total mole number comprises the combination of terephthalic acid and sulfomonomer, supposes that sulfomonomer exists with sour form.In literary composition of the present invention, term " terephthalic acid " comprises use terephthalic acid and corresponding acid anhydrides, ester and acyl chloride derivative.The preferred bis--terephthalate who uses comprises dimethyl terephthalate (DMT) in sulfopolyester of the present invention, yet, also allow to use to comprise more high-grade alkyl ester such as ethyl, propyl group, sec.-propyl and butyl.In addition, also can use aromatic ester, particularly phenyl.Preferably, terephthalic acid component is selected from: terephthalic acid and dimethyl terephthalate (DMT).
As mentioned above, sulfopolyester of the present invention contains the other dicarboxylic acid except terephthalic acid or derivatives thereof or sulfomonomer less than 5mol%.Preferably, sulfopolyester of the present invention does not contain any other acid, and promptly component (ii).The example that can be used as component dicarboxylic acid (ii) comprises aliphatic dicarboxylic acid, ester ring family dicarboxylic acid, aromatic dicarboxylic acid or these two or more sour mixtures.Preferred dicarboxylic includes but not limited to succsinic acid, pentanedioic acid, hexanodioic acid, nonane diacid, sebacic acid, fumaric acid, toxilic acid, methylene-succinic acid, 1; 3-cyclohexane dicarboxylic acid, 1; 4-cyclohexane dicarboxylic acid, diglycollic acid, 2; 5-norbornane dicarboxylic acid, m-phthalic acid, 1; 4-naphthalene dicarboxylic acids, 2,5-naphthalene dicarboxylic acids, diphenic acid, 4,4 '-oxygen base dibenzoic acid and 4; 4 '-, the alkylsulfonyl dibenzoic acid.Term " dicarboxylic acid " comprises the corresponding acid anhydrides of these acid of use, ester and chloride of acid.Compare preferred diester, and dimethyl ester most preferably with acid anhydrides and chloride of acid.Also allow to use and comprise more high-grade alkyl ester such as ethyl, propyl group, sec.-propyl and butyl or the like.In addition, also can consider to use aromatic ester, particularly phenylester.
The polyoxyethylene glycol component (iii) is provided at wetting ability in the sulfopolyester skeleton but the nonionic part.Except the hydrophilic advantage that can modify sulfopolyester, use polyoxyethylene glycol can obtain many other advantages.For example, can realize reducing melt viscosity, improve bonding force and increase wear resistance by concrete glycol moiety.Yet the amount that increases polyoxyethylene glycol (PEG) does not simply cause easily disperse or disperses transparent/stability.When hydrophilic glycol (be PEG component (iii)) combines to be provided at T with hydrophobicity glycol (promptly more hydrophobic than PEG component diol component)
gDuring greater than the best combination of 25 ℃ dispersivenesses, can obtain best effect.The suitable hydrophobicity glycol (be diol component (iv)) that is used for sulfopolyester of the present invention is discussed hereinafter.
When the molecular weight of PEG increased, the bonded maximum reduced.In other words, PEG component molecular weight and molecular fraction (iii) is inversely proportional to mutually.Particularly, when molecular weight increased, the molecular fraction of PEG reduced.Usually, the molecular fraction scope of PEG is about 25 to 90mol% (based on total molecular fractions of hydroxyl equivalent).In a preferred embodiment, the PEG that has molecular weight and be 106 (being n=2) can account for maximum 90mol% of total glycol, is that the PEG of 850 (being n=19) is generally with combined less than the 10mol% of total diol amount and have molecular weight.
The PEG component (iv) has following general formula:
HO-(CH
2CH
2-O)
n-H wherein, n at least 2 but less than 20, preferably, 2≤n≤10 and more preferably 2≤n≤6.It is most preferred that low molecular poly is as glycol ether, triglycol and Tetraglycol 99.
Importantly, will be appreciated that owing to can pass through to change processing condition and control side reaction, but original position generates some glycol (iv).Specific embodiment is because acid-catalyzed dehydration generates glycol ether, triglycol and the Tetraglycol 99 of different ratios by ethylene glycol, when not adding buffer reagent when increasing the pH value of (promptly reducing acid) reaction mixture, is easy to take place acid-catalyzed dehydration.If buffer reagent is saved from ethylene glycol, glycol ether or the ethylene glycol, glycol ether and the triglycol that contain different ratios and bonded charging thereof, then other compositing range is feasible.
As mentioned above, comprise and above-mentioned PEG component (iii) during bonded hydrophobicity glycol the dispersiveness that can be improved when the diol component of sulfopolyester of the present invention.Suitable hydrophobicity glycol, promptly the component of sulfopolyester of the present invention (iv) comprises: aliphatic, alicyclic and aralkyl glycol, and comprise greater than about 10mol% of the total molecular fraction of hydroxyl equivalent to less than about 75mol%.More preferably, diol component (iv) comprises about 20mol% of the total molecular fraction of hydroxyl equivalent to about 50mol%.The example of these glycol comprises: ethylene glycol, propylene glycol, 1, ammediol, 2,4-dimethyl-2-ethyl hexane-1, the 3-glycol, 2,2-ethyl-2-butyl-1, ammediol, 2-ethyl-2-isobutyl--1, ammediol, 1,3 butylene glycol, 1, the 4-butyleneglycol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, 2,2,4-trimethylammonium-1, the 6-hexylene glycol, the sulphur di-alcohol, 1, the 2-cyclohexanedimethanol, 1, the 3-cyclohexanedimethanol, 1, the 4-cyclohexanedimethanol, 2,2,4,4-tetramethyl--1,3-cyclobutanediol and terephthaldehyde's base glycol, preferred ethylene glycol.
For providing the difunctional sulfomonomer of water dispersible, water dispersible sulfopolyester of the present invention is selected from: contain at least one dicarboxylic acid or derivatives thereof that is combined in the sulfonation group on the aromatic ring and contain the alcohol acid or derivatives thereof that at least one is combined in the sulfonation group on the aromatic ring.Favourable difunctional sulfomonomer can be dicarboxylic acid, its ester or from the glycol of dicarboxylic acid or its ester and glycol reaction product, wherein dicarboxylic acid or its ester contain sulfonation group (SO
3M), glycol contains sulfonation group.The positively charged ion of sulfonate can be a metal ion, as Li
+, Na
+, K
+, Mg
++, Ca
++, Cu
++, Ni
++, Fe
+++With similar ion.Nonmetallic sulfonate and the nitrogen base alkali described in United States Patent (USP) 4304901 (its content is hereby incorporated by) are included in the scope of the present disclosure.Suitable nitrogen base base cations is from nitrogenous base, and it can be to have ionization constant (under 25 ℃ in water) 10
-3-10
-10, preferred 10
-5-10
-8Aliphatics, cyclic aliphatic or aromatics.Suitable nitrogenous base for example is ammonia, pyridine, morpholine and piperidines.
Known cationic selection influences the water dispersible of last resulting polymers usually significantly.According to the end-use of polymkeric substance, may need more easily or more to be difficult for the dispersive product.Use as sulfonate sodium, and follow when polymkeric substance is discrete form, replace sodium with ion exchange method, can prepare sulfopolyester with different ions such as zinc.This type of ion exchange method is better than preparing polymkeric substance with divalence and trivalent salt usually, because sodium salt more is soluble in the fusion mutually of polymer reaction thing usually.Ion exchange method is also essential usually to obtain nitrogenous counterion, because amine salt tends to unstable under general melt-processed condition.
Preferred difunctional sulfomonomer is that wherein sulfonation group is combined on the aromatic acid ring those, as benzene, naphthalene, biphenyl, oxydiphenyl base, alkylsulfonyl biphenylyl or methylene radical biphenylyl.More preferably, sulfomonomer is selected from described in the United States Patent (USP) 3779993 (its content is hereby incorporated by): sulfosalicylic phthalate, sulfo group terephthalic acid, sulfoisophthalic acid, 4-sulfo group naphthalene-2,7-dicarboxylic acid and their ester.Even more preferably, difunctional sulfomonomer is 5-sodiosulfoisophthalic acid or its ester.The amount of preferred difunctional sulfomonomer is 6 to 40mol%, more preferably 8 to 30mol% and most preferably 9 to 25mol% (based on total acid equivalent).
The method for preparing sulfopolyester of the present invention comprises two different steps: transesterify or esterification step and condensation polymerization step.Transesterify or esterification step were carried out under 180-230 ℃ 1-4 hour in inert atmosphere, in carrying out under 150-250 ℃ 0.5-8 hour and be preferable over.Usually difunctional sulfomonomer is directly added in the reaction mixture, make polymkeric substance thus.Other method is known, also can utilize.From the case illustrated such as the United States Patent(USP) Nos. 3018272,3075952 and 3033822 of this area, its content is hereby incorporated by.According to the reactivity of glycol and the concrete experiment condition of use, its consumption is every equimolar acid-functional monomer 1.05-2.5mol molar excess usually.Preferably, esterification carries out under greater than environment or atmospheric pressure.Under any situation, inert atmosphere such as nitrogen or argon will produce good effect.Second step referred to polycondensation, decompression, 230-350 ℃, preferred 240-310 ℃ and more preferably carried out preferred 0.25 to 2 hour 0.1-6 hour under 250-290 ℃.In two steps, use and stir or abundant thermal conduction and the surperficial renewal of appropriate condition to guarantee reaction mixture.
Promote reaction in two steps with suitable catalyzer, particularly those catalyzer well known in the art and that said as United States Patent(USP) Nos. 4167395 and 5290631 (its content is hereby incorporated by).Appropriate catalyst includes but not limited to: the salt of alkoxy titanium compound, alkali metal hydroxide and alcoholate, organic carboxyl acid, Alkyzin compound, metal oxide or the like.When using terephthalic acid as one of starting raw material, esterification is autocatalytic.Also can use the three similar step production methods that disclose to U.S. Patent No. 5290631 (its content is hereby incorporated by), particularly when using the mix monomer of acid and ester.Multistep processes also is the process useful of control glycol moiety, and as mentioned above, wherein ethylene glycol, glycol ether, triglycol etc. are by accidental side reaction change.
The preferred buffer reagent that uses prepares sulfopolyester of the present invention.Buffer reagent and uses thereof is well known in the art, and those skilled in the art knows it and is used to prepare sulfopolyester.Preferred reducing agents comprises sodium acetate, potassium acetate, lithium acetate, SODIUM PHOSPHATE, MONOBASIC, dipotassium hydrogen phosphate and yellow soda ash.The amount of buffer reagent is every mole of difunctional sulfomonomer of maximum 0.2mol.Preferably, the amount of buffer reagent is every mole of difunctional sulfomonomer of about 0.1mol.
By under abundant stirring and heating state, fusion or solid-state polymkeric substance are added in the entry, can make the water dispersion of water dispersible sulfopolyester of the present invention.
As mentioned above, because the wear resistance of its improvement and resistance to blocking, the sulfopolyester of water dispersible of the present invention can be used as the textile fibres slurry especially.In addition, the sulfopolyester of water dispersible of the present invention has easily disperse and excellent dispersion shelf-life stability.Thereby an aspect of of the present present invention relates to the paste compound that is used for textile strand that made by linear polyester and with the fibre product of its starching.
When the multifilament polyester yarn is made into textiles, before woven, require with can be at least the bonding and paste compounds processing warp thread that is bonded together of several filaments.This treatment process, i.e. " starching " gives yarn in the woven process with intensity and wear resistance.As a rule, also preferably paste compound is removed from textiles fully, be sometimes referred to as " destarch ".Increase wear resistance and cause line facial cleft line less in the woven process, this has improved the quality and the process velocity of textiles.Though described application is about polyester yarn, as poly-(ethylene terephthalate) or poly-(1,4-hexanaphthene two terephthalic acid methylene esters), composition hereinafter described can be used as the slurry of various natural and synthetic yarns.The example of non-polyester yarn comprises: regenerated fiber, acrylic fibre, polyolefine, cotton yarn, nylon and cellulose acetate.The hybrid yams of polyester and non-polyester yarn is also in can be by the fiberoptic scope of effectively starching.
Therefore, the method that to relate to by the water dispersible sulfopolyester of the present invention that is applied in the water medium in another embodiment of the present invention be the textile strand starching.Usually, textile strand is immersed in the water-bath that contains sulfopolyester of concentration that meets the requirements (as 1-30wt%) and temperature (as 60-100 ℃), makes its draining between the roller by spinning is passed subsequently, last, the line of dry starching in kiln is ready for fibrous bundle woven then.The ordinary method of starching of being used to spin comprises European method, classics or admiralty method and single end sizing or day this law.
In one embodiment, the spinning of starching is through the destarch operation, to remove paste compound before bleaching, dyeing and finishing operation.In another embodiment, for example by using linking agent, make paste compound for good and all be applied to spinning, this is being known in the art, and has report (its content is hereby incorporated by) in United States Patent(USP) Nos. 3767207 and 3666400.
Paste compound of the present invention is a water dispersible, and according to the type of yarn, it comprises about 1 to about 30wt% sulfopolyester of the present invention usually.As known in the field and say, various additives can be added in the paste compound of the present invention as United States Patent(USP) Nos. 3 546 008 (its content is hereby incorporated by).The example of suitable additive comprises: talcum, whitening agent, dyestuff, thickening material, buffer reagent, sterilant and stablizer.
When fiber is wrapped in through axle or bobbin and under envrionment conditions during long storage, paste compound should have enough resistance to blockings and seem very crucial.The fibre fusion that adhesion causes starching together, thereby stoped them in the time that requires, to be untied.The tendency that adhesion takes place under normal and extreme two kinds of envrionment conditionss of temperature and humidity may be directly and the T of paste compound
gRelevant.Therefore, the T under the drying conditions
gBe 25 to 75 ℃, preferred 30 to 65 ℃ and more preferably 35 to 60 ℃ the time, can avoid adhesion problems usually.The T of very high (＞75 ℃)
gUsually represent easily crisp sulfopolyester, it has poor adhesive, manufacturability and wear resistance.Therefore, should consider to select diol component, for example, too the PEG of a large amount can reduce T unfriendly
gAnd cause adhesion.Usually, increase and the molecular fraction that adds when constant the T of final polymkeric substance when the length of polyalkylene glycol monomer or molecular weight
gReduce pro rata.
Desizability and the water tolerance of adhesive power, flexible, part is also relevant with molecular weight and the content of the PEG of sulfopolyester.When PEG content increased, wetting ability, flexible and adhesive power also increased.If PEG content and/or molecular weight are too high, the slurry that then obtains has low T
gWith critical water tolerance.Desizability, water resisting property, flexible also relevant with the content of sulfomonomer with adhesive power.If the amount of sulfomonomer is too high, then water resisting property, economy flexible and slurry reduce, and the low sulfomonomer trend of function reduces adhesive power and dispersiveness, and will stop the fully destarch afterwards of woven operation.
In order to reach best size performance, the limiting viscosity of sulfopolyester is for 0.25dL/g at least with preferably above 0.3dL/g and glass transition temperature (T
g) be at least 25 ℃ and preferred 30-65 ℃.
Therefore, in a preferred embodiment, the T when slurry feedstock of the present invention is drying
gFor 30-65 ℃ and limiting viscosity (under the concentration of about 0.25g polymkeric substance in the 100ml solvent, 25 ℃, measuring in the phenol/tetrachloroethane solution of 60/40 part (weight)) are the water dispersible sulfopolyester of 0.1dL/g at least, it comprises:
(i) terephthalic acid or its derivative,
(ii) less than at least a dicarboxylic acid except terephthalic acid or derivatives thereof or sulfomonomer of about 5mol% (based on the total mole number of acid),
At least a polyoxyethylene glycol that contains following structure of (iii) about 25 to about 90mol% (based on total molecular fractions of hydroxyl equivalent):
H-(OCH
2CH
2) n-OH wherein the molecular fraction and the n value of 2≤n＜20 and the polyoxyethylene glycol that exists be inversely proportional to,
(iv) greater than about 10 to less than the glycol except polyoxyethylene glycol of about 75mol% (based on total molecular fraction of hydroxyl equivalent) or diol mixture and
(what v) content was enough to provide the sulfopolyester water dispersible at least aly is selected from following difunctional sulfomonomer: contain at least one dicarboxylic acid or derivatives thereof that is combined in the sulfonation group on the aromatic ring, contain at least one and be combined in two of sulfonation group on the aromatic ring and pure and mildly contain the alcohol acid or derivatives thereof that at least one is combined in the sulfonation group on the aromatic ring
Wherein, sulfopolyester contains the acid equivalent (about 100mol%) and the hydroxyl equivalent (about 100mol%) of first-class substantially molar ratio, and therefore, the summation of acid and hydroxyl equivalent equals about 200mol%.
Embodiment
Following embodiment to be in order illustrating but not to limit the scope of the invention.The raw material and the experimental technique that are used for result shown here are as follows:
Use the blue obvolvent experimental machine of dupp to measure the fastness to rubbing that goes up sizing, this is well known to those skilled in the art.The blue experiment of dupp is what to carry out on the yarn sample of starching, under constant tension force, yarn is worn and torn so that constant speed is mobile to and fro above yarn by friction disc.Record is the average number cycles of yarn separately, as fastness to rubbing or the blue value of dupp.Therefore, the higher blue value of dupp is the direct indicator of sulfopolyester as the suitability of grout material.
Use difference formula scanning calorimeter (DSC) to measure glass transition temperature (T
g).
Limiting viscosity (IV) is in phenol/tetrachloroethane solution 60/40 part (weight), under 25 ℃, measures under the concentration of about 0.25g polymkeric substance in the 100ml solvent.
Embodiment 1 and 2 has illustrated that the original position of useful diol combination generates.Embodiment 3 has illustrated how buffer reagent is used to control the glycol moiety with respect to material.Embodiment 4 is the preferred embodiments of the invention.Embodiment 5 and 6 is used for contrast jointly, selects suitable glycol for obtaining high T with proof
gThe importance of the polymkeric substance (embodiment 6) of (embodiment 5) and easy processing.Embodiment 7 is comparing embodiments and embodiment 8 is the preferred embodiments of the invention.Embodiment 9 contrasts the fastness to rubbing of the fastness to rubbing of the sulfopolyester of embodiment 1 and commercially available sulfopolyester slurry products.Embodiment 10 is to use the other acid of 5mol% to prepare the embodiment of sulfopolyester.
Embodiment 1
Contain 11mol%5-sodiosulfoisophthalic acid ester and 70mol% blended
The preparation of the water dispersible sulfopolyester of PEG
Material added assembled mat glass head, stir shaft, nitrogen inlet and in the 500mL round-bottomed flask of removing the side arm that volatile matter uses.The material that adds is: the solution of titanium isopropoxide in propyl carbinol of 86.3g (0.445mol) dimethyl terephthalate (DMT), 16.3g (0.055mol) dimethyl-5-sodiosulfoisophthalic acid ester, 36.0g (0.58mol) ethylene glycol, 44.5g (0.42mol) glycol ether and 1.10mL1.03% (w/v).Use the nitrogen purging flask, and flask is immersed in Bel covers in the metal bath at 200 ℃ and kept 70 minutes down, kept other 120 minutes down, fully stir simultaneously and slow nitrogen purging in 210 ℃.Temperature is increased to after 275 ℃, little by little reduces to 0.5mm, and keep other 85 minutes to carry out polycondensation from 760mm 35 minutes internal pressures.Substitute vacuum with nitrogen atmosphere then, before transparent, amber polymkeric substance is shifted out from flask, with its cooling.The limiting viscosity of the recovery polymkeric substance that records according to ASTM D3835-79 is 0.56dL/g.The glycol moiety of NMR analysis revealed reality is the TEG that 30mol%EG, 56mol%DEG and 14mol% generate by side reaction.Analyze the glass transition temperature (T of the polymkeric substance that obtains with DSC heat
g) be 38 ℃.Polymer powder is broken into particle size≤3mm.
Embodiment 2
Contain 11mol%5-sodiosulfoisophthalic acid ester and 82mol% blended
The preparation of the water dispersible sulfopolyester of PEG
Except changing the polycondensation time, use embodiment 1 described device and total process.The inventory that begins to add flask is: the solution of titanium isopropoxide (IV) in propyl carbinol of 86.3g (0.445mol) dimethyl terephthalate (DMT), 16.3g (0.055mol) dimethyl-5-sodiosulfoisophthalic acid ester, 26.7g (0.43mol) ethylene glycol, 60.4g (0.57mol) glycol ether and 1.14mL1.03% (w/v).Under the pressure 0.2mmHg, polycondensation carried out under 275 ℃ 120 minutes.The limiting viscosity of the polymkeric substance that reclaims is that 0.55dL/g (ASTMD3835-79) reaches the dried T that measures with DSC
gIt is 34 ℃.The glycol moiety of NMR analysis revealed reality is 18mol%EG, 68mol%DEG and 14mol%TEG.The polymer powder of glassy yellow is broken into particle size≤3mm.
Embodiment 3
Contain 15mol%5-sodiosulfoisophthalic acid ester and 72mol%DEG
The preparation of water dispersible sulfopolyester
Except changing transesterify and the polycondensation time, using embodiment 1 described device and total process.The reactant of beginning comprises: the solution of titanium isopropoxide (IV) in propyl carbinol of 82.5g (0.425mol) dimethyl terephthalate (DMT), 22.2g (0.075mol) dimethyl-5-sodiosulfoisophthalic acid ester, 11.2g (0.18mol) ethylene glycol, 76.3g (0.72mol) glycol ether, 0.62g (0.0075mol) sodium acetate and 0.44mL1.46% (w/v).Polyesterification is carrying out under 200 ℃ 60 minutes and carried out under 230 ℃ 90 minutes, and condensation polymerization step was carried out 104 minutes under 280 ℃ and 6mmHg subsequently.Limiting viscosity and T with method acquisition same as described above
gValue is respectively 0.39dL/g and 49 ℃.NMR analysis revealed polymeric acid component comprises 85mol% terephthalate and 15mol%5-sodiosulfoisophthalic acid ester units, and diol component comprises 28mol%EG and 72mol%DEG.
Embodiment 4
Prepare the water dispersible sulfopolyester by terephthalic acid
The material adding has been assembled in the 316SS Pa Er high-pressure reactor of agitator, heat transfer coils and distillation column.The material that adds is: 739.6g (4.46mol) terephthalic acid, 147.5g (0.55mol) 5-sodiosulfoisophthalic acid, 446.1g (4.2mol) glycol ether and 360.0g (5.8mol) ethylene glycol.Pressure and the temperature of setting up 40psig with nitrogen kept 60 minutes for 225 ℃, kept 80 minutes down at 245 ℃ then.Remove by the distillation column that remains on 150 ℃ and to anhydrate.The oligopolymer that above-mentioned reaction is made shifts out from the Pa Er reactor, and is transferred to and assembled mat glass head, stir shaft, nitrogen inlet and in the 500mL round-bottomed flask of removing the side arm that volatile matter uses.After with the nitrogen purging flask, the catalyst solution that adds capacity is to provide the titanium of 100ppm.Then reactor leaching is covered in the metal bath Bel and keep 10 minutes down with the fusing oligopolymer, then, before reaching the vacuum of 0.6mm, temperature is increased to 275 ℃ and keep 35 minutes to carry out polycondensation at 225 ℃.Substitute vacuum with nitrogen atmosphere, before polymkeric substance is shifted out from flask, it can be cooled off.Before analyzing, polymer powder is broken into particle size≤6mm.The limiting viscosity that records is 0.73dL/g, and GC analysis revealed glycol moiety is 25mol%EG, 44mol%DEG and 31mol%TEG, and the glass transition temperature of analyzing the polymkeric substance that obtains with DSC heat is 26 ℃.The comparative example 5
Contain 7mol%5-sodiosulfoisophthalic acid ester and TEG
The preparation of water dispersible sulfopolyester
Except transesterify is being carried out under 200 ℃ 60 minutes and carried out under 230 ℃ 90 minutes, and polycondensation is carried out outside 95 minutes under 280 ℃ and 0.5mmHg, uses embodiment 1 described device and total process.The reactant and the amount thereof of beginning are: the solution of titanium isopropoxide (IV) in propyl carbinol of 89.2g (0.46mol) dimethyl terephthalate (DMT), 11.8g (0.04mol) dimethyl-5-sodiosulfoisophthalic acid ester, 150.0g (1.0mol) triglycol, 0.33g (0.004mol) sodium acetate and 0.64mL1.46% (w/v).With the polymkeric substance that methods analyst same as described above reclaims, the limiting viscosity 0.52dL/g of acquisition and T
gValue is 4 ℃.NMR analysis revealed polymkeric substance formation (acid and the diol units of equal quantities contained in total mole number=200) comprises 93mol% terephthalate, 7mol%5-sodiosulfoisophthalic acid ester and 100mol%TEG.The low T of this polymkeric substance
gCause adhesion.When disperseing, obtain product muddy, unstable (being phase-splitting) with 30% solia particle.The comparative example 6
Contain 30mol%5-sodiosulfoisophthalic acid ester and EG
The preparation of water dispersible sulfopolyester
Except transesterify was carried out under 160 ℃ 120 minutes, before 25 minutes internal pressures are reduced to 0.35mmHg gradually, temperature is increased to outside 230 ℃ then, use embodiment 1 described device and total process.After carrying out about 25 minutes polycondensation, stopped reaction when self being wrapped on the agitator owing to the high melt viscosity of polymkeric substance.The reactant that begins to add comprises: 67.9g (0.35mol) dimethyl terephthalate (DMT), 44.4g (0.15mol) dimethyl-5-sodiosulfoisophthalic acid ester, 62.0g (1.0mol) ethylene glycol, 0.5g (0.006mol) sodium acetate, 0.25g weisspiessglanz (III) and 0.25g zinc acetate (II).Limiting viscosity and T with the preceding method acquisition
gValue is respectively 0.11dL/g and 97 ℃.NMR analysis revealed polymer composition comprises terephthalate, 28.5mol%5-sodiosulfoisophthalic acid ester, 91mol%EG and the 9mol%DEG structural unit of 71.5mol%.The high melt viscosity of polymkeric substance will hinder in general device produces, and therefore is not suitable for the present invention.
Embodiment 7 and 8
The comparison of fiber sizing performance
Table 1 is the comparison according to the fiber sizing performance of previous embodiment synthetic polymkeric substance.Two kinds of polymkeric substance all are dispersed in the deionized water with amount of solid 30wt% and suitably dilute being suitable for and isolate.Be used for the dispersive general method and be heating water to 80-90 ℃ and sieve at solid particulate under the good stirring state keeping.
Fiber experiment is to pass (isolating) 150 denier's warp thread and carry out drying and carry out by the paste compound of stretched polyester yarn by water-dispersion.Result in the table 1 shows, adds common acid (being m-phthalic acid) greater than 5mol% and causes slurry to have with the similar compositions that only contains terephthalic acid equating resistance to blocking basically.Embodiment preferred embodiment 8 is than the T of embodiment 7
gLow, this support all is non-palpability and the validity of the sulfopolyester of terephthalate as grout material.As well known to a person skilled in the art, reduce the T of sulfopolyester
gUsually increase the adhesion tendency.Embodiment 7 is in scope of the present invention with outside lecturing, and the sole purpose that its is comprised is to come for these non-obvious instructions are distinguished with prior art, and embodiment 8 is the preferred embodiments of the invention.What be applied to fiber is constant to slurry amount or dry pulp amount to two embodiment basically.
Table 1: resistance to blocking correlation data
*Total acid and glycol=200mole%T=dimethyl terephthalate (DMT) SIP=dimethyl-5-sodiosulfoisophthalic acid ester EG=ethylene glycol DEG=glycol ether TEG=triglycol
| The embodiment sequence number | Form (Mole%) * | ????Tg ???(℃) | % gives the slurry amount | Adhesion |
| ????7 | ?T＝42，I＝16 ?SIP＝11，EG＝47， ?DEG＝33，TEG＝20 | ????42 | ????6.0 | ????2.6 |
| ????8 | ?T＝87，gIP＝13 ?EG＝40，DEG＝40，TEG＝20 | ????37 | ????6.2 | ????2.9 |
Adhesion experiment is carried out by the following method: the yarn of 500 meters starchings is entangled on the bobbin and maintenance 7 days under the condition of 40 ℃ and 90% relative humidity.The mean force that debatching requires is to measure for 25 times/second by in 2 minutes the result of tonometer being sampled, and guarantees highly accurate.3000 readings are average, and final adhesion value provides with voltage.Its value is 0-5, and its value is high more, and the adhesion value is also big more.
Embodiment 9
The fastness to rubbing contrast
The sulfopolyester that makes with the method identical with embodiment 1 carries out the fastness to rubbing contrast with commercially available sulfopolyester slurry products (Eastman WD Size).The result is as shown in table 2, and wherein fastness to rubbing provides with the blue cycle number of dupp that the natural yarns that is used for starching obtains.The fastness to rubbing of known excellence is directly relevant with good woven efficient.
Table 2: fastness to rubbing correlation data
*Total acid and glycol=200mole%T=dimethyl terephthalate (DMT) SIP=dimethyl-5-sodiosulfoisophthalic acid ester EG=ethylene glycol DEG=glycol ether TEG=triglycol
| Embodiment 9 | Form (Mole%) *?T＝89，SIP＝11， ?EG＝31，DEG＝55， ????TEG＝14 | % add-on 9.4 | The blue circulation 73 of dupp |
| ????- | ?Eastman?WD?Size | ????9.1 | ????18 |
Experimental technique comprises: pass test fixture with yarn doubling 20 times, and pass 417 grams back and forth and pluck cotton till the indication fracture.Test is carried out with three circular increment, and any line in fracture and half yarn at least separate interrelated.Cycle number is high more, and fastness to rubbing is just big more.
Embodiment 10
Use the preparation of the water dispersible sulfopolyester of the other acid of maximum 5mol%
Material added assembled mat glass head, stir shaft, nitrogen inlet and in the 1000mL round-bottomed flask of removing the side arm that volatile matter uses.The material that adds is: the solution of titanium isopropoxide in propyl carbinol of 163.0g (0.84mol) dimethyl terephthalate (DMT), 8.3g (0.05mol) m-phthalic acid, 32.6g (0.11mol) dimethyl-5-sodiosulfoisophthalic acid ester, 91.2g (0.86mol) glycol ether, 71.9g (1.2mol) ethylene glycol and 2.34mL 0.98% (w/v).Use the nitrogen purging flask, and flask is immersed in Bel covers in the metal bath at 200 ℃ and kept 70 minutes down, and under the stirring velocity and slow nitrogen purging of 200rpm, kept other 120 minutes down in 210 ℃.Temperature is increased to after 275 ℃, little by little reduces to＜1mm from 760mm 25 minutes internal pressures.Pressure kept 13 minutes under＜1mm, increased to 10mm and kept other 34 minutes with complete polycondensation.Substitute vacuum with nitrogen, before with transparent, flaxen polymer recovery, it can be cooled off.The limiting viscosity of the glassy polymers that obtains is 0.44dL/g (ASTM D3835-79) and does (secondary experiment) T
gIt is 39 ℃.Glycol moiety by hydrolysis GC analysis revealed reality is 32mol%EG, 56mol%DEG and 12mol%TEG.
Claims (20)
1. water dispersible sulfopolyester is measured its limiting viscosity at least O.1dL/g in the phenol/tetrachloroethane solution under the concentration of about 0.25g polymkeric substance in the 100ml solvent, 25 ℃, at 60/40 weight part, it comprises:
(i) terephthalic acid or its derivative,
(ii) based on total molecular fraction of acid, less than at least a dicarboxylic acid except terephthalic acid or derivatives thereof or sulfomonomer of about 5mol%,
(iii) based on total molecular fraction of hydroxyl equivalent, the polyoxyethylene glycol shown in about 25 to about 90mol% at least a following structural formula:
H-(OCH
2CH
2) n-OH wherein the molecular fraction and the n value of 2≤n＜20 and the polyoxyethylene glycol that exists be inversely proportional to,
(iv) based on total molecular fraction of hydroxyl equivalent, greater than about 10 to less than the glycol except polyoxyethylene glycol of about 75mol% or diol mixture and
(what v) content was enough to provide the sulfopolyester water dispersible at least aly is selected from following difunctional sulfomonomer: contain at least one dicarboxylic acid or derivatives thereof that is combined in the sulfonation group on the aromatic ring, contain at least one and be combined in two of sulfonation group on the aromatic ring and pure and mildly contain the alcohol acid or derivatives thereof that at least one is combined in the sulfonation group on the aromatic ring
Wherein, sulfopolyester contains the acid equivalent (about 100mol%) and the hydroxyl equivalent (about 100mol%) of first-class substantially molar ratio, and therefore, the summation of acid and hydroxyl equivalent equals about 200mol%.
2. the sulfopolyester of claim 1, wherein:
Terephthalic acid or derivatives thereof component (i) is selected from: terephthalic acid, dimethyl terephthalate (DMT) and composition thereof,
The dicarboxylic acid component (ii) is selected from: succsinic acid, pentanedioic acid, hexanodioic acid, nonane diacid, sebacic acid, fumaric acid, toxilic acid, methylene-succinic acid, 1; 3-cyclohexane dicarboxylic acid, 1; 4-cyclohexane dicarboxylic acid, diglycollic acid, 2; 5-norbornane dicarboxylic acid, m-phthalic acid, 1,4-naphthalene dicarboxylic acids, 2,5-naphthalene dicarboxylic acids, diphenic acid, 4; 4 '-oxygen base dibenzoic acid and 4; 4 '-, alkylsulfonyl dibenzoic acid and composition thereof
The polyoxyethylene glycol component (iii) in, the n value is 2≤n≤10,
Diol component (iv) is selected from: aliphatic diol, alicyclic diol, aralkyl glycol and composition thereof and
The difunctional sulfomonomer component (v) is to contain the dicarboxylic acid or derivatives thereof that at least one is combined in the sulfonation group on the aromatic ring.
3. the sulfopolyester of claim 1, wherein:
The terephthalic acid or derivatives thereof is selected from terephthalic acid and dimethyl terephthalate (DMT) and its amount greater than 60mol%, based on total acid equivalent,
Polyoxyethylene glycol component (iii) amount is 80-50mol%, and reaching the n value is 2≤n≤6,
Diol component (iv) is selected from: ethylene glycol, propylene glycol, neopentyl glycol, 1, the 2-propylene glycol, 1, ammediol, 2,4-dimethyl-2-ethyl hexane-1, the 3-glycol, 2,2-dimethyl-1, ammediol, 2-ethyl-2-butyl-1, ammediol, 2-ethyl-2-isobutyl--1, ammediol, 1, the 3-butyleneglycol, 1, the 4-butyleneglycol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, 2,2,4-trimethylammonium-1, the 6-hexylene glycol, the sulphur di-alcohol, 1, the 2-cyclohexanedimethanol, 1, the 3-cyclohexanedimethanol, 1, the 4-cyclohexanedimethanol, 2,2,4,4-tetramethyl--1,3-cyclobutanediol and p-Xylol glycol, and its amount is 20 to 50mol%, based on total hydroxyl equivalent and
Difunctional sulfomonomer is selected from: sulfo group phthalic acid and ester thereof, sulfo group terephthalic acid and ester, sulfoisophthalic acid and ester thereof, 4-sulfo group naphthalene-2,7-dicarboxylic acid and ester thereof, 5-sodiosulfoisophthalic acid and ester thereof and their mixture, and its amount is about 6 to about 40mol%, based on total acid equivalent.
4. the sulfopolyester of claim 1, wherein said sulfopolyester does not conform to any dicarboxylic acid except terephthalic acid or derivatives thereof or sulfomonomer.
5. the sulfopolyester of claim 3, wherein: difunctional sulfomonomer is 5-sodiosulfoisophthalic acid or its ester, and its amount is about 8 to about 30mol%, based on total acid equivalent.
6. the sulfopolyester of claim 5, wherein: the difunctional sulfomonomer amount is about 9 to about 25mol%, based on total acid equivalent.
7. the sulfopolyester of claim 1, wherein: glycol, component (v), is selected from glycol ether, triglycol and Tetraglycol 99.
8. the sulfopolyester of claim 1, wherein: limiting viscosity is 0.25dL/g and T at least
gBe at least 25 ℃.
9. the sulfopolyester of claim 1, wherein: limiting viscosity is 0.3dL/g and T at least
gBe 25-75 ℃.
10. the sulfopolyester of claim 1, wherein: T
gBe 30-65 ℃.
11. paste compound, it comprises the sulfopolyester of about claim 1 of 1 to about 25wt%.
12. fibre product with the paste compound starching of the water dispersible sulfopolyester that comprises claim 1.
13. have limiting viscosity with comprising (under the concentration of about 0.25g polymkeric substance in the 100ml solvent, 25 ℃, in the phenol/tetrachloroethane solution of 60/40 part (weight), measure) be the fibre product of the paste compound starching of the water dispersible sulfopolyester of 0.1dL/g at least, this sulfopolyester comprises:
(i) terephthalic acid or its derivative,
(ii) based on total molecular fraction of acid, less than at least a dicarboxylic acid except terephthalic acid or derivatives thereof or sulfomonomer of about 5mol%,
(iii) based on total molecular fraction of hydroxyl equivalent, the polyoxyethylene glycol shown in about 25 to about 90mol% at least a following structural formula:
H-(OCH
2CH
2) n-OH wherein the molecular fraction and the n value of 2≤n＜20 and the polyoxyethylene glycol that exists be inversely proportional to,
(iv) based on total molecular fraction of hydroxyl equivalent, greater than about 10 to less than the glycol except polyoxyethylene glycol of about 75mol% or diol mixture and
(what v) content was enough to provide the sulfopolyester water dispersible at least aly is selected from following difunctional sulfomonomer: contain at least one dicarboxylic acid or derivatives thereof that is combined in the sulfonation group on the aromatic ring, contain at least one and be combined in two of sulfonation group on the aromatic ring and pure and mildly contain the alcohol acid or derivatives thereof that at least one is combined in the sulfonation group on the aromatic ring
Wherein, sulfopolyester contains the acid equivalent (about 100mol%) and the hydroxyl equivalent (about 100mol%) of first-class substantially molar ratio, and therefore, the summation of acid and hydroxyl equivalent equals about 200mol%.
14. the fibre product of claim 13, wherein: the T of paste compound
gBe 0.25dL/g at least greater than 25 ℃ and limiting viscosity.
15. the fibre product of claim 13, wherein: the T of paste compound
gBe about 30 to about 65 ℃.
16. the fibre product of claim 13, wherein: the T of paste compound
gBe about 35 to about 60 ℃.
17. the fibre product of claim 13, wherein: the limiting viscosity of sulfopolyester is greater than 0.3dL/g.
18. the method for textile strand starching comprises: textile strand with the paste compound of the water dispersible sulfopolyester that comprises claim 1 of the significant quantity of said textile strand starching can be contacted.
19. the method for claim 18 is further comprising the steps of: the textile strand of woven starching, then with the textile strand destarch of starching to remove paste compound.
20. the method for claim 18, wherein, paste compound permanently is applied on the textile strand.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11080898P | 1998-12-03 | 1998-12-03 | |
| US60/110808 | 1998-12-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1333792A true CN1333792A (en) | 2002-01-30 |
Family
ID=22335057
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99815831 Pending CN1333792A (en) | 1998-12-03 | 1999-12-03 | Terephthalate-based sulfopolyesters |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP1135426A1 (en) |
| JP (1) | JP2002531612A (en) |
| CN (1) | CN1333792A (en) |
| BR (1) | BR9915893A (en) |
| WO (1) | WO2000032672A1 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798761A (en) * | 2010-04-28 | 2010-08-11 | 东华大学 | Sizing agent applied to high-count single-warp and single-weft worsted fabric warp yarn and preparation method thereof |
| CN102816313A (en) * | 2012-07-24 | 2012-12-12 | 苏州市华元化工有限公司 | Polyester slurry and production method thereof |
| CN102828414A (en) * | 2012-09-20 | 2012-12-19 | 吴江福华织造有限公司 | Viscose rayon environment-friendly size for water-spraying weaving |
| CN104371096A (en) * | 2014-12-05 | 2015-02-25 | 安徽皖维高新材料股份有限公司 | Sea-island fiber water-soluble polyester and preparation method thereof |
| CN104672437A (en) * | 2015-03-02 | 2015-06-03 | 中国乐凯集团有限公司 | Waterborne polyester with high refractive index and preparation of waterborne polyester |
| CN105669959A (en) * | 2015-06-06 | 2016-06-15 | 青岛科技大学 | Water-soluble polyester and preparation method thereof |
| CN113372545A (en) * | 2021-06-29 | 2021-09-10 | 宜昌中盈科技发展有限公司 | Low-melting-point water-soluble polyester and preparation method thereof |
| CN113617232A (en) * | 2021-08-30 | 2021-11-09 | 安徽清澜新材料科技有限公司 | Reverse osmosis membrane non-woven fabric supporting material coated with modified polyester powder and preparation method thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955581B (en) * | 2010-10-10 | 2012-06-06 | 四川宏扬高分子科技有限公司 | Water-soluble polyester slurry prepared from waste polyester plastics and preparation method thereof |
| US8580872B2 (en) * | 2011-07-21 | 2013-11-12 | Eastman Chemical Company | Sulfopolyester polymer compositions with improved water dispersibility |
| JP6279896B2 (en) * | 2013-12-24 | 2018-02-14 | 日本合成化学工業株式会社 | Polyester resin and polyester resin aqueous liquid |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2438379C3 (en) * | 1974-08-09 | 1978-09-21 | Cassella Farbwerke Mainkur Ag, 6000 Frankfurt | Polyesters which are readily soluble or dispersible in water, their preparation and use |
| EP0709419B1 (en) * | 1994-10-24 | 2004-04-14 | Eastman Chemical Company | Water-dispersible block copolyesters |
| US5646237A (en) * | 1995-08-15 | 1997-07-08 | Eastman Chemical Company | Water-dispersible copolyester-ether compositions |
| DE19533797A1 (en) * | 1995-09-13 | 1997-03-20 | Basf Ag | Water-dispersible polyester useful for sizing polyester filaments on all weaving looms |
-
1999
- 1999-12-03 WO PCT/US1999/028542 patent/WO2000032672A1/en not_active Application Discontinuation
- 1999-12-03 BR BR9915893-0A patent/BR9915893A/en not_active Application Discontinuation
- 1999-12-03 CN CN 99815831 patent/CN1333792A/en active Pending
- 1999-12-03 EP EP99961916A patent/EP1135426A1/en not_active Withdrawn
- 1999-12-03 JP JP2000585312A patent/JP2002531612A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798761A (en) * | 2010-04-28 | 2010-08-11 | 东华大学 | Sizing agent applied to high-count single-warp and single-weft worsted fabric warp yarn and preparation method thereof |
| CN102816313A (en) * | 2012-07-24 | 2012-12-12 | 苏州市华元化工有限公司 | Polyester slurry and production method thereof |
| CN102828414A (en) * | 2012-09-20 | 2012-12-19 | 吴江福华织造有限公司 | Viscose rayon environment-friendly size for water-spraying weaving |
| CN104371096A (en) * | 2014-12-05 | 2015-02-25 | 安徽皖维高新材料股份有限公司 | Sea-island fiber water-soluble polyester and preparation method thereof |
| CN104672437A (en) * | 2015-03-02 | 2015-06-03 | 中国乐凯集团有限公司 | Waterborne polyester with high refractive index and preparation of waterborne polyester |
| CN105669959A (en) * | 2015-06-06 | 2016-06-15 | 青岛科技大学 | Water-soluble polyester and preparation method thereof |
| CN105669959B (en) * | 2015-06-06 | 2019-04-19 | 青岛科技大学 | A kind of water-soluble polyester and preparation method thereof |
| CN113372545A (en) * | 2021-06-29 | 2021-09-10 | 宜昌中盈科技发展有限公司 | Low-melting-point water-soluble polyester and preparation method thereof |
| CN113617232A (en) * | 2021-08-30 | 2021-11-09 | 安徽清澜新材料科技有限公司 | Reverse osmosis membrane non-woven fabric supporting material coated with modified polyester powder and preparation method thereof |
| CN113617232B (en) * | 2021-08-30 | 2022-07-22 | 安徽清澜新材料科技有限公司 | Reverse osmosis membrane non-woven fabric supporting material coated with modified polyester powder and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| BR9915893A (en) | 2001-08-21 |
| JP2002531612A (en) | 2002-09-24 |
| WO2000032672A1 (en) | 2000-06-08 |
| EP1135426A1 (en) | 2001-09-26 |
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