DK156137B - PROCEDURE FOR THE PREPARATION OF WATER SOLUBLE, SULPHONATED POLYESTERS - Google Patents
PROCEDURE FOR THE PREPARATION OF WATER SOLUBLE, SULPHONATED POLYESTERS Download PDFInfo
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- DK156137B DK156137B DK387273A DK387273A DK156137B DK 156137 B DK156137 B DK 156137B DK 387273 A DK387273 A DK 387273A DK 387273 A DK387273 A DK 387273A DK 156137 B DK156137 B DK 156137B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/918—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/507—Polyesters
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- 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
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- Polymers & Plastics (AREA)
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- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Polyesters Or Polycarbonates (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
DK 156137 BDK 156137 B
Den foreliggende opfindelse angâr en fremgangsmâde til fremstilling af hidtil ukendte, vandoplpselige polyestre, som fremstilles ved sulfonering af umættede polyestres dobbeltbindinger.The present invention relates to a process for the preparation of novel water-soluble polyesters produced by the sulfonation of unsaturated polyesters double bonds.
5 Opfindelsen angâr endvidere en anvendelse af disse polyestre som vandoplpselige slettemidler til tekstilgarner.The invention further relates to the use of these polyesters as water-soluble erasers for textile yarns.
Det er ved vævning n0dvendigt at anvende slettemidler, da det er umuligt at væve med en trâd med svag snoning, idet en sâdan trâd har 10 en utilstrækkelig modstandsdygtighed mod slid under vævningen, og disse slettemidler skal kunne fjernes med vand inden farvningen. Man forspger nu at væve med en trâd, der kun har den snoning, som gives af spindemaskinen, dvs. 10 til 15 vindinger pr. meter. De vandopld-selige produkter ifplge opfindelsen har i denne forbindelse vist sig 15 meget fordelagtige.When weaving, it is necessary to use erasers, as it is impossible to weave with a thread with a slight twist, since such a thread has an insufficient resistance to abrasion during weaving and these erasers must be removable with water before dyeing. It is now proposed to weave with a thread having only the twist given by the spinning machine, ie. 10 to 15 turns per meters. The water-soluble products of the invention have proved very advantageous in this connection.
Fra JP patentskrift nr. 10167/68 kendes en fremgangsmâde til frem-stilling af letfarvelige polyestergarner ved ganske let sulfonering af garnet med svovlsyrling i en vandopldselig ether som opl0snings-20 middel.JP Patent No. 10167/68 discloses a process for preparing light-dyed polyester yarns by quite easily sulfonating the yarn with sulfuric acid in a water-soluble ether as the solvent.
Fra DE offentliggprelsesskrift nr. 1.816.163 kendes der vandoplese-lige slettemidler pâ polyesterbasis, som indeholder sulfonerede aromatiske rester.DE publication publication 1,816,163 discloses water-soluble polyester-based erasers containing sulfonated aromatic residues.
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Endelig kendes der fra US patentskrift nr. 2.028.091 estersulfone-rede carbonsyrer, der pâ grund af deres overfladeaktive egenskaber egner sig til emulgeringsmidler og detergenter.Finally, US Patent No. 2,028,091 discloses estersulfonated carboxylic acids which, due to their surfactant properties, are suitable for emulsifiers and detergents.
30 Det er kendt, at man kan fremstille en lang række umættede polyestre med et meget bredt anvendelsesomrâde ved polykondensation af en polyol med en umættet dicarboxylsyre, eventuelt i nærværelse af en mættet dicarboxylsyre. Sk0nt de fremkomne harpikser er i besiddelse af egenskaber, der er gunstige til mange formâl, har de imidlertid 35 den mangel, at de er uopldselige i vand, hvilket begrænser deres anvendelse pâ omrâder, hvor denne egenskab er af fundamental betyd-ning.It is known that a wide variety of unsaturated polyesters having a very wide range of applications can be prepared by polycondensing a polyol with an unsaturated dicarboxylic acid, optionally in the presence of a saturated dicarboxylic acid. However, although the resulting resins possess properties favorable to many purposes, they have the disadvantage of being insoluble in water, limiting their application to areas where this property is of fundamental importance.
Formâlet med opfindelsen er at afhjælpe ovennævnte mangler og atThe object of the invention is to overcome the above-mentioned shortcomings and to
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2 tilvejebringe nye hidtil ukendte polyestre, hvis anvendelse er særdeles fordelagtig ti1 de forskellige anvendelsesmuligheder.2 provide new novel polyesters, the use of which is very advantageous for the various applications.
Den foreliggende opfindelse angâr sâledes tre fremgangsmâder til 5 fremstilling af hidtil ukendte, vandoplpselige, sulfonerede polyestre, som bestàr af rester af aromatiske dicarboxylsyrer, sulfonerede aliphatiske dicarboxylsyrer og mættede glycoler. Disse fremgangsmâder er ejendommelige ved, at enten polykondenseres 10 A) 1) dimethylterephthalat, dimethylisophthalsyre eller isophthalsyre, 2} dimethylmaleat, maleinsyreanhydrid eller itaconsyre, 15 3} di- og/eller triethylenglycol, hvorhos molforholdet mellem 1) og 2) er pâ fra 90:10 til 70:30, og det opnâede produkt sulfoneres med natriumbisulfit eller natrium-metabisulfit, eller ogsâ polykondenseres 20 B) 1) isophthalsyre, 2) natriumsaltet af dimethylsulfosuccinat, 25 3) diethylenglycol, hvorhos molforholdet mellem 1) og 2) er pâ fra 95:5 til 50:50, eller ogsâ polykondenseres 30 C) 1) isophthalsyre, 2) en oplosning, der er opnâet ved sulfonering af et mol bis-(diethylenglycol)maleat i vand med 0,4 mol natriummeta-bisulfit og efterfplgende fortynding med vand, 35 3) diethylenglycol, hvorhos der til et mol isophthal syre anvendes 736 g af en 50% oplpsning eller 117 g af en 80% oplpsning.The present invention thus relates to three processes for the preparation of novel, water-soluble, sulfonated polyesters consisting of residues of aromatic dicarboxylic acids, sulfonated aliphatic dicarboxylic acids and saturated glycols. These processes are characterized by either polycondensing 10 A) 1) dimethyl terephthalate, dimethylisophthalic acid or isophthalic acid, 2} dimethyl maleate, maleic anhydride or itaconic acid, 3} di- and / or triethylene glycol, wherein the molar ratio of 1) to 2) is from 90 : 10 to 70:30, and the product obtained is sulfonated with sodium bisulfite or sodium metabisulfite, or also polycondensated 20 B) 1) isophthalic acid, 2) the sodium salt of dimethylsulfosuccinate, 3) diethylene glycol, wherein the molar ratio of 1) to 2) is on from 95: 5 to 50:50, or also polycondensated 30 C) 1) isophthalic acid, 2) a solution obtained by sulfonating a mole of bis- (diethylene glycol) maleate in water with 0.4 mole of sodium metasulphite and subsequent dilution with water; 3) diethylene glycol using 736 g of a 50% solution or 117 g of an 80% solution for one mole of isophthalic acid.
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DK .156-137 BDK .156-137 B
At denne sulfonering udelukkende sker ved de umættede bindinger, nâr sulfoneringen udf0res pâ kondensationsproduktet (udfprelsesform A), kan pâvises analytisk ved infrar0d spektroskopi.That this sulphonation occurs only by the unsaturated bonds when the sulphonation is performed on the condensation product (Embodiment A) can be demonstrated analytically by infrared spectroscopy.
5 De polyestre, som fremkommer ved den forudgâende kondensation af de forskellige reaktanter fulgt af sulfonering af de alifatiske dob-beltbindinger, er vanskeligere at fremstille pâ grund af den store viskositet af polymerforbindelsen ved 100°C, ved hvilken temperatur sulfonering almindeligvis gennemfpres, men denne vanskelighed kan 10 overvindes ved hensigtsmæssige tekniske processer.The polyesters resulting from the prior condensation of the various reactants followed by sulfonation of the aliphatic double bonds are more difficult to prepare due to the high viscosity of the polymeric compound at 100 ° C, at which temperature sulfonation is commonly passed, but this difficulty can be overcome by appropriate technical processes.
Ved den forudgâende sulfonering af diesteren af den alifatiske umættede dicarboxylsyre fulgt af reaktion mellem denne sulfonerede diester og de to andre reaktanter, sâledes at den vandoplpselige 15 sulfonerede polyester fremkommer direkte, undertrykkes de ovennævnte viskositetsulemper til gengæld fuldstændigt. Ved denne fremgangsmâde kan man endvidere fâ polyestre med et stort indhold af sulfonerede grupper netop pâ grund af, at viskositetsproblemer under sulfoneringen undgàs.In the preceding sulphonation of the diester of the aliphatic unsaturated dicarboxylic acid followed by reaction between this sulphonated diester and the other two reactants so that the water-soluble sulphonated polyester appears directly, the above viscosity disadvantages, in turn, are completely suppressed. In addition, this method can obtain polyesters with a high content of sulphonated groups precisely because the viscosity problems during sulphonation are avoided.
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Sulfonering direkte pâ den umættede alifatiske dicarboxylsyre eller dennes anhydrid lader sig vanskeligt gennemfpre og giver utilfreds-stillende udbytter, hvilket i praksis bevirker, at sulfoneringen udelukkende foretages pâ diesteren af den umættede alifatiske 25 disyre.Sulfonation directly on the unsaturated aliphatic dicarboxylic acid or its anhydride is difficult to effect and gives unsatisfactory yields, which in effect causes the sulfonation to be carried out exclusively on the diester of the unsaturated aliphatic diacid.
Som aromatiske dicarboxylsyrer anvender man isophtalsyre, dimethylterephthalat og dimethylisophthalat.As aromatic dicarboxylic acids, isophthalic acid, dimethyl terephthalate and dimethyl isophthalate are used.
30 Som umættede alifatiske dicarboxylsyrekomponenter anvender man dimethylmaleat, maleinsyreanhydrid og itaconsyre.As unsaturated aliphatic dicarboxylic acid components dimethyl maleate, maleic anhydride and itaconic acid are used.
Som glycoler anvender man diethylenglycol og/eller triethylenglycol.Diethylene glycol and / or triethylene glycol are used as glycols.
35 Ved fremstillingen af disse polyestre udfpres kondensationen under de klassiske reaktionsbetingelser med opvarmning i 2-5 timer, idet temperaturen hæves jævnt til 220-270°C, og reaktanterne anvendes i st0kiometriske mængder eller med et mindre overskud af én af disse.In the preparation of these polyesters, the condensation is expressed under the classic reaction conditions with heating for 2-5 hours, raising the temperature evenly to 220-270 ° C and using the reactants in stoichiometric amounts or with a slight excess of one.
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Sulfonering udfpres derpâ ved en middeltemperatur mellem 20 og 100°C og med en varighed, som almindeligvis ligger mellem 3 og 6 timer, i nærværelse af en lille mængde vand og ved atmosfæretryk eller under tryk. Som sulfoneringsmiddel anvendes fortrinsvis 5 natriumbisulfit eller natriummetabisulfit, da disse midler er virksomme over for de alifatiske kæders umættethed. Der anvendes sulfoneringsmiddel i en mængde, som er stdkiometrisk ækvivalent med mængden af umættet dicarboxylsyre.Sulfonation is then expressed at an average temperature between 20 and 100 ° C and with a duration generally between 3 and 6 hours, in the presence of a small amount of water and at atmospheric pressure or under pressure. As the sulfonating agent, sodium bisulphite or sodium metabisulphite is preferably used as these agents are effective against the unsaturation of the aliphatic chains. Sulfonating agent is used in an amount which is stoichiometric equivalent to the amount of unsaturated dicarboxylic acid.
10 Denne sulfonering af diestre af alifatiske umættede dicarboxylsyrer udf0res ved en middeltemperatur mellem 20 og 100°C og med en varighed af 1-3 timer i nærværelse af vand ved atmosfæretryk eller under tryk. Som sulfoneringsmiddel anvendes fortrinsvis natriumbisulfit eller natriummetabisulfit.This sulfonation of diesters of aliphatic unsaturated dicarboxylic acids is carried out at an average temperature between 20 and 100 ° C and for a duration of 1-3 hours in the presence of water at atmospheric pressure or under pressure. As the sulfonating agent, sodium bisulfite or sodium metabisulfite is preferably used.
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Reaktionsbetingelserne for den efterfplgende kondensation til dannelse af de sulfonerede polyestre er de klassiske betingelser med opvarmning i 2-15 timer, en temperatur, som stiger jævnt til 180-250°C, og under anvendelse af reaktanterne i st0kiometriske 20 mængder eller med et mindre overskud af én af disse.The reaction conditions for the subsequent condensation to form the sulfonated polyesters are the classic conditions with heating for 2-15 hours, a temperature which rises evenly to 180-250 ° C, and using the reactants in stoichiometric amounts or with a small excess. of one of these.
Der gives herefter eksempler pâ uddvelse af opfindelsen.Examples are then given of the practice of the invention.
A) Forudgâende kondensation af de forskellige bestanddele efter-25 fulgt af senere sulfoneringA) Preliminary condensation of the various components followed by subsequent sulfonation
Eksempel 1Example 1
Kondensation 30 I en reaktor pâ 0,5 liter forsynet med omrprer og svaler anbringes fplgende reaktanter: dimethylisophtalat 174,6 g 35 dimethylmaleat 14,4 g diethylenglycol 111,0 g isopropyl-o-titanat 0,3 mlCondensation 30 In a 0.5 liter reactor equipped with stirrer and cooler, the following reactants are placed: dimethyl isophthalate 174.6 g of dimethyl maleate 14.4 g of diethylene glycol 111.0 g of isopropyl o-titanate 0.3 ml
Der opvarmes ved atmosfæretryk under omrpring og svag gennemstr0m-It is heated at atmospheric pressure during stirring and weak throughput.
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5 ning af nitrogen, idet temperaturen hæves jævnt fra 20 til 220°C i Ipbet af 2 timer, hvorefter 60 g methanol udvindes.Of nitrogen, raising the temperature evenly from 20 to 220 ° C over the course of 2 hours, after which 60 g of methanol is recovered.
Kondensationen fortsættes under vakuum pâ 266 Pa med en temperatur-5 stigning fra 220 til 260°C i Ipbet af 30 minutter. Denne temperatur og dette tryk holdes ½ time, hvilket er den npdvendige tid til at fuldende kondensationen og til at fjerne overskydende diethylenglycol.The condensation is continued under vacuum at 266 Pa with a temperature rise from 220 to 260 ° C over the 30 minute period. This temperature and pressure are kept for ½ hour, which is the time needed to complete the condensation and to remove excess diethylene glycol.
10 Der afkples til 100°C, inden vakuumet brydes for at undgâ oxidation af maleinsyrens dobbeltbindinger.Cool to 100 ° C before breaking the vacuum to avoid oxidation of the maleic acid double bonds.
Sulfonerina 15 Til den fremkomne polyester sætter man, under omrpring og ved 100°C: 9,5 g natriummetabisulfit i pulverform 20 ml destilleret vand tilsat over 30 minutter ved hjælp af en tildrypningstragt.Sulfonerina 15 To the resulting polyester, under stirring and at 100 ° C, 9.5 g of powdered sodium metabisulfite are added 20 ml of distilled water added over 30 minutes by means of a dropping funnel.
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Der opvarmes med tilbagesvaling (ca. 110°C) i 2 timer.Reflux (approx. 110 ° C) for 2 hours.
Der fremkommer et gult, uigennemsigtigt produkt, som indeholder ca.A yellow opaque product appears, containing approx.
7% vand og som ved normal temperatur er et fast stof. Dette dis-25 pergeres i varmt vand under omrpring og giver derved en uigen-nemsigtig oplpsning.7% water and which at normal temperature is a solid. This is dispersed in hot water while stirring, thereby providing an opaque solution.
Grænseviskositetstallet η for det tprre produkt var: 0,23 dl/g (grænseviskositetstallet η er bestemt ved 0,25% og 25°C i en 30 oplpsning bestâende af 60 g phénol og 40 g tetrachlorethan).The intrinsic viscosity η for the tighter product was: 0.23 dl / g (the intrinsic viscosity η is determined at 0.25% and 25 ° C in a solution of 60 g of phenol and 40 g of tetrachloroethane).
Eksempel 2Example 2
Under de i eksempel 1 angivne reaktionsbetingelser (for kondensation 35 og sulfonering) gentages forspget, idet diethylenglycol erstattes med triethylenglycol.Under the reaction conditions set forth in Example 1 (for condensation 35 and sulfonation), the bias is repeated, replacing diethylene glycol with triethylene glycol.
Man har da fplgende reaktanter:You have the following reactants:
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6 dimethylisophtalat 174,6 g dimethylmaleat 14,4 g triethylenglycol 157,5 g tetraisopropyl-o-titanat 0,3 ml 56 dimethyl isophthalate 174.6 g dimethyl maleate 14.4 g triethylene glycol 157.5 g tetraisopropyl o-titanate 0.3 ml
Sulfoneringsulfonation
Til det fremkomne produkt sættes, som angivet i eksempel 1: 10 natriummetabisulfit 9,5 g vand 20 mlTo the resulting product, as indicated in Example 1: 10 sodium metabisulphite, 9.5 g of water are added 20 ml
Der fremkommer et mprkegult produkt, som endog efter tdrring er blpdt og klæbende.A pale yellow product appears, which even after drying is soft and sticky.
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Grænseviskositetstal η: 0,38 dl/g.Intrinsic viscosity η: 0.38 dl / g.
Produktet er oplpseligt i varmt vand.The product is soluble in hot water.
20 En 20% oplpsning er hvid. Den omdannes til gel ved afkpling.20 A 20% resolution is white. It is converted to gel by decoupling.
Eksempel· 3Example · 3
Under de i eksempel 1 angivne reaktionsbetingelser gentages fors0-25 get, idet dimethylisophtalat erstattes med dimethylterephtalat, hvorpâ der sulfoneres ved trykket 2 bar, og en temperatur pâ ca.Under the reaction conditions set forth in Example 1, the test is repeated, replacing dimethyl isophthalate with dimethyl terephthalate, which is sulfonated at 2 bar pressure, and a temperature of approx.
130°C.130 ° C.
Man har da fplgende reaktanter: 30 ' dimethylterephtalat 174,6 g dimethylmaleat 14,4 g diethylenglycol 159,0 g tetraisopropyl-o-titanat 0,3 ml 35The following reactants are then obtained: 30 'dimethyl terephthalate 174.6 g dimethyl maleate 14.4 g diethylene glycol 159.0 g tetraisopropyl o-titanate 0.3 ml
Sulfoneringsulfonation
Til det fremkomne produkt sættes, som angivet i eksempel 1:To the resulting product is added as indicated in Example 1:
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7 natriummetabisulfit 9,5 g vand 20 ml7 sodium metabisulphite 9.5 g water 20 ml
Der arbejdes i en rustfri reaktor under et tryk pâ 2 bar ved 5 temperaturen 130°C og en varighed af forspget pâ 2 timer.A stainless steel reactor is operated under a pressure of 2 bar at 5 temperature 130 ° C and a duration of 2 hours.
Der fremkommer et temmeligt hàrdt, gult uigennemsigtigt produkt, som er opl0seligt i varmt vand. En 10% opldsning er hvid og viskds. Den omdannes til gel ved afkoling.A fairly hard yellow opaque product appears, which is soluble in hot water. A 10% charge is white and viscous. It is converted to gel upon decarburization.
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Eksempel 4Example 4
Kondensationen udfdres under de betingelser, som er beskrevet i eksempel 1, men sulfoneringen gennemfpres med en 15 natriumbisulfitoplosning. Den anvendte fremgangsmâde er folgende: dimethylisophtalat 136,0 g dimethylmaleat 43,0 g diethylenglycol 106,0 g 20 tetraisopropyl-o-titanat 0,3 mlThe condensation is carried out under the conditions described in Example 1, but the sulfonation is effected with a sodium bisulfite solution. The procedure used is as follows: dimethyl isophthalate 136.0 g dimethyl maleate 43.0 g diethylene glycol 106.0 g tetraisopropyl o-titanate 0.3 ml
SulfonerinaSulfonerina
Til den ovennævnte polyester sættes, idet temperaturen holdes ved 25 100°C, under temmelig hurtig omrpring, 400 ml 50/50 oplosning af natriumbisulfit ved 36° Bé og destilleret vand.To the above polyester is added, keeping the temperature at 100 ° C, with fairly rapid stirring, 400 ml of 50/50 solution of sodium bisulfite at 36 ° Bé and distilled water.
Tilsætningen varer 1 time.The addition lasts 1 hour.
30 Temperaturen og omrpringen opretholdes i 4 timer.The temperature and ambient temperature are maintained for 4 hours.
Efter afkpling til 50°C udskilles ved centrifuger!ng to lag. Det organiske lag, som ligger underst, er den sulfonerede polyester med et vandindhold pâ 30%.After cooling to 50 ° C, two layers are separated by centrifugation. The organic layer at the bottom is the sulphonated polyester with a water content of 30%.
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Grænseviskositetstallet η: 0,23 dl/g.The limit viscosity η: 0.23 dl / g.
Produktet er opldseligt i varmt vand, idet der dannes en svagt uklar oplpsning.The product is biodegradable in warm water, forming a slightly cloudy solution.
Eksempel 5Example 5
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Med let modificerede forspgsbetingelser gentages fremgangsmâden fra eksempel 1. Dimethylisophtalat er her erstattet med isophtalsyre, og 5 en inhibitor for polymerisationen er tilsat.With slightly modified bias conditions, the procedure of Example 1 is repeated. Dimethyl isophthalate is here replaced with isophthalic acid and an inhibitor for the polymerization is added.
Kondensation I en reaktor pâ 2 liter forsynet med omrprer og svaler anbringes: 10 isophtalsyre 747 g maleinsyreanhydrid 49 g diethylenglycol 1060 g 2,5-ditertiobutyl-hydroquinon 1 g 15 tetraisopropyl-o-titanat 1,5 mlCondensation In a 2 liter reactor equipped with stirrer and cooler are placed: 10 isophthalic acid 747 g maleic anhydride 49 g diethylene glycol 1060 g 2,5-ditertiobutyl hydroquinone 1 g 15 tetraisopropyl o-titanate 1.5 ml
Der opvarmes ved atmosfæretryk under omrpring og svag luftning med nitrogen, idet temperaturen hæves jævnt fra 20 til 225°C i l0bet af l\ time. Kondensationen fortsættes under et vakuum pâ 266 Pa, idet 20 temperaturen hæves fra 225 til 240°C i lpbet af 1½ time. Der afk0les til 140°C, hvorpâ vakuumet brydes.It is heated at atmospheric pressure under stirring and gentle aeration with nitrogen, raising the temperature evenly from 20 to 225 ° C over 1 hour. The condensation is continued under a vacuum of 266 Pa, raising the temperature from 225 to 240 ° C over a period of 1½ hours. Cool to 140 ° C, whereupon the vacuum breaks.
Sulfonerina 25 Ved 100°C sættes under omrpring f0lgende til den dannede polyester: natriummetabisulfit 50 g vand 100 ml (tilsat i lpbet af 1 time) 30Sulfonerina 25 At 100 ° C, add the following to the polyester formed: sodium metabisulphite 50 g water 100 ml (added over 1 hour)
Temperaturen holdes ved 100°C i 3 timer.The temperature is kept at 100 ° C for 3 hours.
Der fremkommer et produkt, som er oplpseligt i varmt vand, idet der dannes en svagt uklar oplpsning.A product is soluble in hot water, forming a slightly cloudy solution.
Grænseviskositetstallet η for det tprre produkt var: 0,19 dl/g.The intrinsic viscosity number η for the tighter product was: 0.19 dl / g.
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Eksemoel 6Example 6
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Den umættede disyre.er her itaconsyre.The unsaturated diacetic acid is itaconic acid.
5 KondensationCondensation
Til en reaktor pâ 0,5 liter forsynet med omrprer og svaler sættes: isophtalsyre 133 g 10 itaconsyre 26 g diethylenglycol 212 g 2,5-ditertiobutylhydroquinon 0,5 g tetraisopropylorthotitanat 0,3 ml 15 Der opvarmes under omr0ring og svag luftning med nitrogen, idet temperaturen hæves fra 20 til 220°C i lpbet af 1\ time. Temperaturen 220°C holdes i en halv time, hvorefter temperaturen ved et vakuum pà 266 Pa hæves fra 220 til 235°C. Man genvinder 34 g vand og 100 g diethylenglycol.To a 0.5 liter reactor equipped with stirrer and cooler is added: isophthalic acid 133 g 10 itaconic acid 26 g diethylene glycol 212 g 2,5-ditertiobutyl hydroquinone 0.5 g tetraisopropyl orthotitanate 0.3 ml Heat under stirring and gentle aeration with nitrogen, raising the temperature from 20 to 220 ° C over the course of 1 hour. The temperature is maintained at 220 ° C for half an hour, after which the temperature is raised from 220 to 235 ° C in a vacuum of 266 Pa. 34 g of water and 100 g of diethylene glycol are recovered.
2020
SulfonerinqSulfonerinq
Ved temperaturen 100°C sættes under omrpring fplgende til den fremkomne polyester: 25 natriummetabisulfit 20 g vand 20 ml (tilsat i l0bet af 1 time) 30 Temperaturen holdes pâ 100°C i 6 timer under fortsat omrdring.At the temperature of 100 ° C, the following polyester is added under stirring: 25 sodium metabisulphite 20 g water 20 ml (added over 1 hour) 30 The temperature is kept at 100 ° C for 6 hours with continued stirring.
Produktet tdrres 48 timer i varmeskab ved 105°C.The product is dried for 48 hours in a heat cabinet at 105 ° C.
Der fremkommer et svagt farvet produkt, som er letopldseligt i vand, 35 idet der dannes en næsten gennemsigtig opl0sning.A slightly colored product appears which is readily soluble in water, forming an almost transparent solution.
Grænseviskositetstallet η for det t0rre produkt var: 0,16 dl/g.The intrinsic viscosity number η for the dry product was: 0.16 dl / g.
Eksempel 7 1°Example 7 1 °
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Under de i eksempel 1 nævnte betingelser gentages fors0get, idet der dog anvendes en blanding af diethylenglycol og triethylenglycol 5 (50/50).Under the conditions mentioned in Example 1, the experiment is repeated, however, using a mixture of diethylene glycol and triethylene glycol 5 (50/50).
Kondensation I en reaktor pà 0,5 liter forsynet med omrprer og svaler anbringes: 10 dimethylisophtalat 873 g dimethylmaleat 72 g diethylenglycol 265 g triethylenglycol 413 g 15 tetraisopropyl-o-titanat 1,5 mlCondensation Into a 0.5 liter reactor equipped with stirrer and cooler is placed: 10 dimethyl isophthalate 873 g dimethyl maleate 72 g diethylene glycol 265 g triethylene glycol 413 g 15 tetraisopropyl o-titanate 1.5 ml
Der opvarmes ved atmosfæretryk under omr0ring og svag luftning med nitrogen, idet temperaturen hæves jævnt fra 20 til 225°C i l0bet af î\ time, hvorefter temperaturen ved et vakuum pâ 266 Pa hæves jævnt 20 til 250°C, ligeledes i l0bet af l\ time. Nâr temperaturen er faldet til 120°, brydes vakuumet. Man har da genvundet: methanol 280 g triethylenglycol 35 g 25It is heated at atmospheric pressure with stirring and gentle aeration with nitrogen, raising the temperature evenly from 20 to 225 ° C over one hour, then raising the temperature in a vacuum of 266 Pa evenly to 20 to 250 ° C, also for 1 \ hour. When the temperature drops to 120 °, the vacuum breaks. Methanol was then recovered: 280 g of triethylene glycol 35 g of 25
SulfonerinqSulfonerinq
Til den fremkomne polyester sættes ved 100°C under omrdring: 30 natriummetabisulfit 50 g vand 100 g (tilsat i l0bet af 1 time)To the resulting polyester is added at 100 ° C with stirring: 30 sodium metabisulphite 50 g water 100 g (added over 1 hour)
Temperaturen 100/105°C holdes i 5 timer.The temperature 100/105 ° C is kept for 5 hours.
3535
Der fremkommer et gult, uigennemsigtigt produkt, som er letopl0se-ligt i varmt vand. En 20% oplpsning er uigennemsigtig og viskps.There is a yellow opaque product which is easily soluble in hot water. A 20% solution is opaque and viscous.
Grænseviskositetstallet η for det t0rre produkt var: 0,23 dl/g.The intrinsic viscosity number η for the dry product was: 0.23 dl / g.
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1111
De sulfonerede vandoplpseüge polyestre, som fremstilles ifplge opfindelsen, udviser egenskaber, som er intéressante i forbindelse med flere anvendelsesomrâder.The sulfonated water-soluble polyesters produced in accordance with the invention exhibit properties which are of interest in several applications.
5 Pâ grund af disse særlige kvaliteter er deres fremtid inden for tekstilomrâdet og i særdeleshed inden for det omrâde, som udgpres af de sâkaldte slettemidler, meget lovende, hvilket allerede er nævnt i beskrivelsens indledning.5 Because of these special qualities, their future in the field of textiles and in particular in the field expressed by the so-called erasers is very promising, as already mentioned in the introduction.
10 Efter gamme! praksis var den snoning, som den kontinuerte fibertrâd fik, betragtelig, af stprrelsesordenen adskilüge hundrede oindre j-ninger pr. meter, hvorved denne trâd fik en tilstrækkeüg stor modstand mod "afslidningen" til, at der kunne væves med den. Men fabrikationsomkostningerne for at opnâ denne snoning steg. Man har 15 derfor spgt at undgâ denne procès ved efterhânden at erstatte den med en sletning, der er lige sa virksom som en snoning af trâden, samtidig med, at den er billigere. Man er nu nàet frem til en minimal snoning pâ 10 til 15 vindinger pr. meter, som udelukkende bibringes af spindemaskinerne. Men i dette tilfælde viser de 20 konventionelle slettemidler sig utilstrækkelige til at give den trâd, som fremkommer ved spindingen, en modstand mod "afslidningen", som gpr det muligt for vævningen at foregâ under gode vilkâr.10 After the gamma! In practice, the twisting obtained by the continuous fiber thread was considerable, of the order of several hundred ounces. meters, giving this thread a sufficient resistance to the "wear" to weave with it. But the fabrication costs to achieve this twist increased. It has therefore been suggested that 15 avoid this process by gradually replacing it with a deletion that is as effective as twisting the tree, while at the same time being cheaper. A minimum twist of 10 to 15 turns per hour is now reached. meters provided solely by the spinning machines. But in this case, the 20 conventional erasers prove insufficient to give the thread resulting from the spinning a resistance to the "wear" which allowed the weaving to take place under good conditions.
Forskellige produkter, sâsom homopolymerer af acrylsyre eller 25 methacrylsyre er blevet anbefalet. Sk0nt gode resultater er opnâet med visse fibre, sâsom viskose, celluloseacetat, nylon, er dette ikke tilfældet med fibre af terephtalsyrepolyestre (indregistrerede mærker er Terylen, Tergal). Det lader til, at der i dette tilfælde er en manglende affinitet mellem fiberen og slettemidlet. For at 30 opnâ en sammenhæng fibrene imellem, som er tilstrækkeüg god til vævning, har man mâttet anvende polymerer, som giver smidige film, sâsom copolymererne ethylacrylat-acrylsyre. Imidlertid bliver disse film let thermoklæbende ved 40°C, deres mekaniske modstand er svag, hvilket bevirker en temmelig dârlig modstand mod "afslidningen". De 35 kraftige gnidningspâvirkninger, som trâden udsættes for under vævningen, bl.a. i vævestolens vævekam, afriver limpartikler og forârsager en stpvet afsætning pâ de maskindele, som styrer trâden, og denne afsætning omdannes hurtigt til en tæt masse, som klæber til métal!et. Det lykkes dog at væve polyestertrâden, sâfremt derVarious products such as homopolymers of acrylic acid or methacrylic acid have been recommended. Although good results have been obtained with certain fibers, such as viscose, cellulose acetate, nylon, this is not the case with fibers of terephthalic acid polyesters (registered marks are Terylene, Tergal). It seems that in this case there is a lack of affinity between the fiber and the eraser. In order to achieve a coherence between the fibers which are sufficiently good for weaving, polymers which provide flexible films, such as the copolymers ethyl acrylate-acrylic acid, have been used. However, these films become slightly thermosetting at 40 ° C, their mechanical resistance is weak, causing a rather poor resistance to "wear". The 35 strong rubbing effects to which the thread is subjected during weaving, i.a. in the loom comb of the loom, glue particles and cause a moldy deposit on the machine parts that control the thread, and this deposit quickly transforms into a dense mass that adheres to the metal. However, it succeeds in weaving the polyester thread, if there
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12 regelmæssigt foretages en rensning af kammen, maskerne og de pinde, soin ski lier lagene.12, the comb, masks and sticks are cleaned regularly.
Hyppigheden af denne vask kan komme op pâ én vask hver 16. eller 24.The frequency of this wash can come up to one wash every 16 or 24.
5 time, nâr det drejer sig om tætvævet stof. For at afhjælpe denne ubehagelige tilsmudsning af vævestolen foràrsaget af limafsætnin-ger er det blevet foreslàet og ogsâ gennemfprt, ud over slettemidlet at afsætte en smorende voks pâ trâden for at mindske gnidningsmod-standen og derved delvis undgà afrivning af slettemidlet fra trâden.5 hours when it comes to tightly woven fabric. In order to remedy this uncomfortable soiling of the loom caused by glue deposits, it has been proposed and also implemented, in addition to depositing a lubricating wax on the tree to reduce the rubbing resistance, thereby partially avoiding tearing the eraser.
1010
Disse voksprodukter er effektive, nâr det drejer sig om normalt eller lostvævet stof, men giver ingen tilfredsstillende losning, nâr det drejer sig om tunge stoffer. Endvidere er de voksarter, som ud fra denne betragtning er mest effektive, oftest produkter, som det 15 er vanskeligt at fjerne inden farvning, da de mâ være sâ hydrofobe som muligt og indeholde mindst muligt overfladeaktiv emulgator, hvis deres smprende egenskaber skal bevares.These wax products are effective in the case of normal or loosely woven fabrics but do not provide a satisfactory solution in the case of heavy fabrics. Furthermore, the waxes which are the most effective from this point of view are most often products which are difficult to remove prior to staining, as they must be as hydrophobic as possible and contain the least possible surfactant emulsifier if their lubricating properties are to be preserved.
For en trâd med 300 vindinger pr. meter er den mængde slettemiddel 20 (torstof), som oftest anvendes til polyestertrâden, af stprrelses-ordenen mindst 3-4% beregnet pâ vægtbasis, hvilket npdvendiggo.r,. at koncentrationen i badet med det aktive stof er 6-8% (pâ vægtbasis).For a thread with 300 turns per meters, the amount of detergent 20 (dry matter) most commonly used for the polyester yarn is of the order of magnitude at least 3-4% by weight, which is necessary. the concentration in the bath of the active substance is 6-8% (by weight).
25 For en trâd, som spindemaskinen har givet en snoning pâ 10 til 15 vindinger pr. meter, er denne mængde slettemiddel utilstrækkelig; det er nddvendigt at pge koncentrationen i bade med det aktive stof til 10% (vægtbasis) for at opnâ 5% t0rstof (vægtbasis) pâ rende-garnet.25 For a thread that has been spun by 10 to 15 turns per spin. meters, this amount of detergent is insufficient; it is necessary to increase the concentration in baths with the active substance to 10% (weight basis) in order to obtain 5% dry matter (weight basis) on the gutter.
3030
Denne forpgelse af belastningen 0ger i lige sâ h0j grad tilsmudsningen af vævestolens dele; dette er en af grundene til den sjældne anvendelse af polyestertrâcf uden torsion til rendegarn.This prejudice of the load increases to the same degree the soiling of the parts of the loom; this is one of the reasons for the rare use of polyester tracf without torsion for gill nets.
35 Anvendelse af ifolge opfindelsen fremstillede produkter som slettemidler gpr det muligt at râde bod pâ de ovenfor beskrevne mangler. Desuden kan disse produkter som f0lge af en bedre vedhæftning anvendes i mindre mængder og alligevel yde en bedre beskyttelse mod "afslidningen".Use of products manufactured in accordance with the invention as remedies makes it possible to remedy the deficiencies described above. Furthermore, as a result of better adhesion, these products can be used in smaller quantities and yet provide better protection against "wear".
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1313
Der er gennemfort fors0g med rendegarn med 40 trâde pr. cm af en Tergal®-trâd (varemærke for "la Société Rhône Poulenc Textile") pâ 65 denier pr. 33 strenge (1 denier = 0,05 g pr. 900 m garn). Dette rendegarn er blevet neddyppet i en vandig oplpsning indeholdende en 5 type slettemiddel bestâende af produktet fra eksempel 1 og derpâ straks presset mellem to cylindre og torret. Der er udfort forsog med 3 bade med slettemiddel indeholdende henholdsvis 3, 4 og 6% aktivt stof (pâ vægtbasis).Tests have been carried out with 40 threads per twine. cm of a Tergal® thread (trademark of "la Société Rhône Poulenc Textile") of 65 denier per 33 strands (1 denier = 0.05 g per 900 m yarn). This gutter has been immersed in an aqueous solution containing a type of eraser consisting of the product of Example 1 and immediately pressed between two cylinders and dried. Experiments have been carried out with 3 baths with a detergent containing 3, 4 and 6% of active substance respectively (by weight).
10 Det sâledes behandlede rendegarn er herefter blevet bearbejdet pâ en væv til taftvævning med 34 slag pr. cm. En korrekt vævning uden brud blev gennemfort, idet beskyttelsen af trâden var bedre, desto mere koncentreret badet med slettemiddel var. I aile 3 tilfælde forekom der efter 50 meter ingen sletteafsætninger pâ vævekammen.10 The reindeer yarn thus treated has subsequently been worked on a fabric for fabric weaving at 34 strokes per minute. cm. Proper weaving without breakage was performed, the better the protection of the thread, the more concentrated the bath with detergent. In all three cases, no erosion deposits occurred on the loom comb after 50 meters.
1515
Sammenligningsforsdg med vævning med samme rendegarn behandlet med tilgængelige kommercielle produkter, sâsom GEROL ACR fra "Société Soprosoie", har vist, at disse ydede utilstrækkelig modstand mod "afslidningen", idet trævler blev afrevet under vævningen, og en 20 bemærkelsesværdig afsætning af slettemiddel pâ kammen optrâdte efter vævning af 50 meters længde.Comparative experiments with weaving with the same reindeer yarn treated with available commercial products, such as GEROL ACR from "Société Soprosoie", have shown that these provided insufficient resistance to "wear", with ribbons being torn off during weaving and a remarkable deposition of detergent on the comb. occurred after weaving of 50 meters in length.
Ved ekstraktion med destilleret vand i Soxhlet-apparat i ammoniakalsk miljp og bestemmelse af torstof i dette vaskevand har 25 man kunnet pâvise, at den mængde slettemiddel (som torstof), der afsættes pâ trâden, normalt svarede til halvdelen af koncentrationen i badet, hvilket vil sige, at et bad med 3% (vægtbasis) aktivt stof gav en afsætning pâ 1,5% (vægtbasis) pâ trâden. Dette er blevet bekræftet af den mængde af det fortyndede bad, som af trâden er 30 blevet fort med over pâ slettemaskinen, eftersom det er blevet pâvist, at 1 kg trâd medbragte ca. 500 g fortyndet bad.By extraction with distilled water in Soxhlet apparatus in ammonia environment and determination of solids in this wash water, it has been shown that the amount of detergent (such as solids) deposited on the stove normally corresponds to half the concentration in the bath, which will say that a bath with 3% (weight basis) of active substance gave a 1.5% weight (weight basis) on the tree. This has been confirmed by the amount of the diluted bath, which has been removed from the tree over onto the eraser machine, since it has been shown that 1 kg of wire brought about. 500 g diluted bath.
Den nye type sletning, baseret pâ produkter ifplge opfindelsen, frembyder væsentlige fordele ved vævning med polyestertrâd, idet 35 denne vævning med hensyn til udbytter og kvalitet kan sammenlignés med det, man opnâr med tekstilfibre sâsom nylon og viskose, hvor sietningsbehandlingen let udfores.The new type of wiping, based on products according to the invention, offers significant advantages in weaving with polyester yarn, as this weaving in terms of yields and quality can be compared to that obtained with textile fibers such as nylon and viscose where the sewing treatment is easily performed.
Slettemidler ifolge opfindelsen har ligeledes givet intéressanteErasers according to the invention have also yielded interest
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14 resultater anvendt pà trâde af celluloseacetat og cellulosetriacetat under forudsætning af, at snoningen af disse trâde var mindst 80 vindinger pr. meter. For en trâd pâ 110 decitex pr. 24 strenge (1 tex = 1 g/1000 m) har disse trâde f.eks. under anvendelse af 5 vinylpolymerer indtil videre ikke udvist vanskeligheder ved vævningen, dels soin fplge grund af, at tilsmudsning af vævestolen overhovedet ikke finder sted. Pâ grund af fabrikationspriserne har man i nogen tid planlagt vævning med trâd med en ringe snoning, eksempelvis 5-15 vindinger pr. meter, sâsom polyestertrâd. Med de 10 sædvanlige produkter skal badet med slettemiddel hâve en koncen-tration pâ 6-7% tprstof beregnet pà vægtbasis for at afsætte 4-5% tirstof (pâ vægtbasis) pâ fibrene, hvilket er den npdvendige mængde til en normal beskyttelse af trâden med "afslidning". Det mâ frem-hæves, at denne belægningsgrad synes at være en minimalværdi uden 15 nævneværdig sikkerhedsmargin, for vævningen er kun antagelig pâ den udtrykkelige betingelse, at der anvendes en trâd af en særlig god kvalitet, hvilket betyder, at den ikke mâ indeholde fiberbestand-dele, soin er knækket pâ hovedstolen eller de spoler, der forsyner trendingens spolestativ.14 results used on traces of cellulose acetate and cellulose triacetate assuming that the twists of these strands were at least 80 turns per second. meters. For a thread of 110 decitex pr. 24 strands (1 tex = 1 g / 1000 m) have these strands e.g. using 5 vinyl polymers so far has not shown any difficulties in the weaving, partly due to the fact that the weaving chair does not get dirty at all. Because of the fabrication prices, weaving has been planned for some time with threads with a slight twist, for example 5-15 turns per day. meters, such as polyester thread. With the 10 usual products, the detergent bath must have a concentration of 6-7% of dry matter calculated on a weight basis to deposit 4-5% of dry matter (by weight) on the fibers, which is the required amount for a normal protection of the tree with "abrasion". It must be emphasized that this coating degree appears to be a minimum value without a significant safety margin, for the weaving is only presumably on the express condition that a thread of a particularly good quality is used, which means that it must not contain any fiber stock. parts, soin are cracked on the principal or the coils that supply the trending coil rack.
2020
Der er blevet vævet med en celluloseacetattrâd pâ 110 decitex pr. 24 strenge og 10 vindinger/meter pâ et kædegarn med en tæthed pâ 40 trâde pr. centimeter og 28 "omgange skudgarn" pr. centimeter. Badet med slettemiddel indeholdt 4% tprstof beregnet pâ vægtbasis af det 25 produkt, som fremkom ved fremgangsmâden ifplge eksempel 1. Der blev iagttaget en korrekt "vævelighed", som var fuldt ud ækvivalent med, hvad man opnâede ved sletning i et bad indeholdende 6% tprstof af et hidtil benyttet vinylpolymerprodukt, som hidtil har været kendt som et effektivt slettemiddel over for celluloseacetattrâde. Til sam-30 menligning har man forspgt at fremstille et identisk kædegarn, som er behandlet i et bad med slettemiddel indeholdende "Gerol ACR" fra "la Société Soprosoie" i en koncentration pâ 4% tprstof beregnet pâ vægtbasis. Vævningen var yderst vanskelig, idet stadig indgriben var nddvendig for at reparere eller fjerne de af trâdens fiberbestand-35 dele, der knækkede pâ grund af den slidende virkning, som forârsa-gedes af den indbyrdes gnidning mellem trâdene og af gnidningen mod vævestolens dele.Woven with a cellulose acetate thread of 110 decitex per 24 strands and 10 turns / meter on a chain yarn with a density of 40 threads per second. centimeters and 28 "rounds of shotgun" per centimeter. The detergent bath contained 4% dry matter calculated on the weight of the product obtained by the method of Example 1. A correct "waviness" was observed which was fully equivalent to what was obtained by deleting in a bath containing 6% test substance of a hitherto used vinyl polymer product which has hitherto been known as an effective antifouling agent for cellulose acetate thread. For comparison, it has been predicted to produce an identical warp yarn which is treated in a detergent bath containing "Gerol ACR" from "la Société Soprosoie" at a concentration of 4% by weight calculated on a weight basis. The weaving was extremely difficult, with intervention still needed to repair or remove those fibers of the thread that broke due to the abrasive effect caused by the inter-rubbing between the threads and the rubbing against the weave parts.
De oplpselige estre ifdlge opfindelsen udviser ligeledes storThe soluble esters of the invention also exhibit large
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15 effektivitet over for trâde pâ basis af celluloseestre. André tekstilfibre sâsom eksempelvis viskose, acrylfibre, polyamidfibre, glasfibre eller fibre pâ basis af polyvinylchlorid kan med gunstigt résultat slettebehandles med forbindelserne fremstillet ifplge 5 opfindelsen.15 against cellulose esters wiring. Other textile fibers such as, for example, viscose, acrylic fibers, polyamide fibers, glass fibers or fibers based on polyvinyl chloride can, with favorable results, be treated with the compounds according to the invention.
II) Forudgâende sulfonering af diesteren af den umaettede alifatiske disvre efterfulot af kondensation af de forskellige bestanddele.II) Prior sulphonation of the diester of the unsaturated aliphatic acid followed by condensation of the various constituents.
10 Der gives fdrst et eksempel pâ fremstilling af et sulfoneret dérivât ud fra dimethylmaleat, idet der efter sulfonering dannes dimethylsulfosucci nat.An example of a sulfonated derivative from dimethyl maleate is first given, with dimethylsulfosuccinate formed after sulfonation.
Til en kolbe pâ 20 liter forsynet med opvarmningsudstyr, propelom-15 rprer, svaler og tildrypningstragt sættes: dimethylmaleat 20 mol (2883 g) eller 2,5 liter vand 80 mol (1440 g) 20 Omrpreren sættes i gang, og der fremkommer en mælket oplpsning. I tildrypningstragten, som er anbragt over kolben, anbringes: natriummetabisulfit 10 mol (1900 g) vand 220 mol (3960 g) 25To a 20 liter flask equipped with heating equipment, propeller mixer, swallower and drip funnel are added: dimethyl maleate 20 mol (2883 g) or 2.5 liter water 80 mol (1440 g) 20 The stirrer is started and a milk is obtained. oplpsning. Into the drip funnel placed over the flask are: sodium metabisulphite 10 moles (1900 g) water 220 moles (3960 g) 25
Temperaturen i kolben hæves fprst til 95°C, hvorpâ tildrypnings-tragtens indhold tilsættes i delportioner pâ 300' - 500 ml pâ en sâdan mâde, at temperaturen holdes mellem 93 og 98°C. Nâr hele oplpsningen af natriummetabisulfit er tilsat (hvilket varer ca. 50 30 minutter) hæves temperaturen og holdes pâ 100°C i endnu en time. Udbyttet ved reaktionen er 98%. Efter udkrystallisation i Ipbet af en nat filtreres pâ sintret glas. Herved fâs i et udbytte pâ 51% af et produkt, som tprres ved 60°C i et ventileret tprreskab.The temperature of the flask is first raised to 95 ° C, whereupon the contents of the drip funnel are added in sub-portions of 300 '- 500 ml in such a way that the temperature is kept between 93 and 98 ° C. When all of the solution of sodium metabisulphite is added (which lasts about 50 30 minutes), the temperature is raised and kept at 100 ° C for another hour. The yield of the reaction is 98%. After crystallization in overnight, filter on sintered glass. This results in a yield of 51% of a product pressed at 60 ° C in a ventilated pressure cabinet.
35 Der gives nu en række eksempler pâ udfdrelsesformer for opfindelsen under anvendelse af dimethylsulfosuccinat fremstillet som ovenfor beskrevet.35 A number of examples of embodiments of the invention are now given using dimethyl sulfosuccinate prepared as described above.
I en reaktor anbringes:In a reactor is placed:
Eksempel 8 16Example 8 16
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5 isophtalsyre 315,4 g dimethylsulfosuccinat (natriumsalt) 24,8 g diethylenglycol 233,2 g tetraisopropyl-o-titanat 0,6 ml 10Isophthalic acid 315.4 g dimethyl sulfosuccinate (sodium salt) 24.8 g diethylene glycol 233.2 g tetraisopropyl o-titanate 0.6 ml
Under nitrogengennemledning hæves temperaturen fprst hurtigt fra 20 til 160°C, hvilket varer omtrent en time, derefter langsommere fra 160 til 200°C pà tre timer. Temperaturen 200°C holdes endnu to timer.Under nitrogen conduction, the temperature first increases rapidly from 20 to 160 ° C, which lasts about one hour, then slower from 160 to 200 ° C in three hours. The temperature 200 ° C is kept for another two hours.
15 I denne période udtrækkes omkring 55 ml af en blanding af vand og methanol. Herefter udvindes ved et tryk pâ 266 til 399 Pa, og stadig ved 200°C, overskud af diethylenglycol (omtrent 20 ml), hvilket varer 2 til 3 timer. Polyesteren, som er flydende, medens den er 20 varm, foreligger pâ fast, vandfri form.During this period, about 55 ml of a mixture of water and methanol are extracted. Then, at a pressure of 266 to 399 Pa, and still at 200 ° C, excess diethylene glycol (about 20 ml) is recovered, which lasts for 2 to 3 hours. The liquid polyester, while warm, is in solid, anhydrous form.
En vandig 30% oplpsning af det fremkomne produkt har et mælket udseende. Blandingen phénol-tetrachlorethan med 0,25% produkt har et grænseviskositetstal η pâ 0,15 dl/g.An aqueous 30% solution of the resulting product has a milky appearance. The mixture of phenol-tetrachloroethane with 0.25% product has an intrinsic viscosity η of 0.15 dl / g.
2525
André karakteristika er f0lgende: syretal IA = 41,8 mg KOH/g 30 hydroxyltal Iq^ = 5,16 mg KOH/g antalsmiddelmolvægt Mn = 2200 g/mol svovlindhold i den frem- 35 komne polymer S(%) » 0,83 (teoretisk 0,67)Other characteristics are as follows: acid number IA = 41.8 mg KOH / g hydroxyl number Iq = 5.16 mg KOH / g number average molecular weight Mn = 2200 g / mol sulfur content of the resulting polymer S (%) »0.83 (theoretical 0.67)
Eksempel 9 I en reaktor anbringes:Example 9 In a reactor is placed:
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17 isophtalsyre 315,4 g dimethylsulfosuccinat (natriumsalt) 24,8 g diethylenglycol 212,2 g 5 tetraisopropyl-o-titanat 0,6 ml17 isophthalic acid 315.4 g dimethyl sulfosuccinate (sodium salt) 24.8 g diethylene glycol 212.2 g tetraisopropyl o-titanate 0.6 ml
Arbejdsbetingelserne for kondensationsreaktionen er de samme som angivet i eksempel 8.The working conditions of the condensation reaction are the same as given in Example 8.
10 En vandig 20% oplosning af det fremkomne produkt har et mælket udseende, men bliver vandklar efter neutralisering med NH^OH.An aqueous 20% solution of the resulting product has a milky appearance but becomes water-clear after neutralization with NH 2 OH.
André karakteristika er fplgende: 15 grænseviskositetstal η 0,22 dl/g IA 34,3 mg KOH/g % 0Other characteristics are as follows: 15 intrinsic viscosity η 0.22 dl / g IA 34.3 mg KOH / g% 0
Mn 3150 g/mol (i stedet for 2200 g/mol i eksempel 1) 20 S (%) 0,71 (teoretisk 0,67)Mn 3150 g / mol (instead of 2,200 g / mol in Example 1) 20 S (%) 0.71 (theoretical 0.67)
Eksempel 10 I en reaktor anbringes: 25 isophtalsyre 305,5 g dimethylsulfosuccinat (natriumsalt) 39,7 g diethylenglycol 233,2 g 30 tetraisopropyl-o-titanat 0,6 mlExample 10 Into a reactor: 25 isophthalic acid 305.5 g dimethylsulfosuccinate (sodium salt) 39.7 g diethylene glycol 233.2 g tetraisopropyl o-titanate 0.6 ml
Arbejdsbetingelserne for kondensationsreaktionen er de samme som i eksempel 8, idet den maksimale temperatur dog er 190°C.The working conditions of the condensation reaction are the same as in Example 8, however, the maximum temperature is 190 ° C.
35 En vandig 20% oplosning er uigennemsigtig, men bliver gennemsigtig efter neutralisering (NH^OH). Den har tendens til at danne en uigennemsigtig gel efter nogle dages opbevaring. Geldannelsen er reversibel ved opvarmning til 70°C.An aqueous 20% solution is opaque but becomes transparent after neutralization (NH4 OH). It tends to form an opaque gel after a few days of storage. The gel formation is reversible upon heating to 70 ° C.
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André karakteristika er fplgende: grænseviskositetstal η 0,13 dl/g IA 27,7 mg KOH/g 5 31,9 mg KOH/gOther characteristics are as follows: limit viscosity η 0.13 dl / g IA 27.7 mg KOH / g 5 31.9 mg KOH / g
Mn 1750 g/mol S (%) 1,02 (teoretisk: 1,06)Mn 1750 g / mol S (%) 1.02 (theoretical: 1.06)
Eksempel 11 10 I en reaktor anbringes: isophtalsyre 289,0 g dimethylsu!fosucci nat 15 (natriumsalt) 64,5 g diethylenglycol 233,2 g tetraisopropyl-o-titanat 0,6 mlExample 11 10 Into a reactor is placed: isophthalic acid 289.0 g of dimethylsulfosuccinate (sodium salt) 64.5 g of diethylene glycol 233.2 g of tetraisopropyl-o-titanate 0.6 ml
Arbejdsbetingelserne for kondensationsreaktionen er de samme som i 20 eksempel 8.The working conditions of the condensation reaction are the same as in Example 8.
Den fremkomne harpiks er praktisk taget ufarvet og skpr. En 30% vandig oplpsning er fuldstændig glasklar.The resulting resin is practically uncoloured and skr. A 30% aqueous solution is completely clear.
25 André karakteristika er fplgende: grænseviskositetstal η 0,16 dl/g IA 15,9 mg KOH/g I0H 20,8 mg KOH/g 30 Mn 2850 g/mol S (%) 1,71 (teoretisk: 1,71)Other characteristics are as follows: intrinsic viscosity η 0.16 dl / g IA 15.9 mg KOH / g IOH 20.8 mg KOH / g 30 Mn 2850 g / mol S (%) 1.71 (theoretical: 1.71)
Eksempel 12 35 Dette eksempel omhandler samme forbindelse som Eksempel 11, men forbindelsen er fremstillet i et anlæg i halvstor skala og uden overskud af glycol.Example 12 35 This example deals with the same compound as Example 11, but the compound is prepared in a plant on a half-scale scale and without excess glycol.
I en glasreaktor pâ 40 liter af typen Pfaudler, som er forsynet medIn a 40 liter glass reactor of the type Pfaudler, which is equipped with
DK 156137 BDK 156137 B
19 en kolonne med samler, omrdrer og indfpringssted for nitrogen, anbringes under omr0ring udgangsstofferne i fdlgende mængder: diethylenglycol 10,610 kg 5 tetraisopropyl-o-titanat 30 ml dimethylsulfosucci nat (natriumsalt) 3,224 kg isophtalsyre 14,442 kg 10 Der opvarmes under omrpring (med en omrpringshastighed indstillet til 150 omdr. pr. minut og en nitrogengennemstrpmning pâ 90 1/time).19, a column of collector, stirrer and nitrogen injection site is placed while stirring the starting materials in the following amounts: diethylene glycol 10,610 kg of tetraisopropyl-o-titanate 30 ml of dimethylsulfosuccinate (sodium salt) 3.224 kg of isophthalic acid under heating (under heating) set to 150 rpm and a nitrogen flow rate of 90 l / h).
Temperaturstigning fra 20 til 200°C foregâr over otte timer. Denne temperatur holdes endnu to timer, inden der sættes vakuum pâ. Luft-15 udpumpningen skal være jævn, for at undgâ voldsom medrivning af uomsatte reaktanter. Trykket nedsættes fra 1 bar til 2000 Pa i lpbet af ½ time, hvorefter det holdes mellem 1333 og 2000 Pa i 5-6 timer med en svag gennemstrpmning af nitrogen (n0dvendig for stripningen af ikke omsatte reaktanter).Temperature rise from 20 to 200 ° C takes place over eight hours. This temperature is kept for another two hours before vacuum is applied. Air-15 pumping must be smooth to avoid excessive entrainment of unreacted reactants. The pressure is reduced from 1 bar to 2000 Pa over the course of ½ hour, after which it is maintained between 1333 and 2000 Pa for 5-6 hours with a low flow of nitrogen (necessary for the stripping of unreacted reactants).
2020
Temperaturen holdes pâ 200°C.The temperature is kept at 200 ° C.
Efter at atmosfæretryk er genetableret, fjernes f0rst det ved kondensationen dannede vand, (4,2 liter), hvorefter produktet 25 udhældes i bakker med teflonbelægning, som forhindrer harpiksens vedhæftning.After atmospheric pressure is restored, the condensed water (4.2 liters) is first removed, after which the product 25 is poured into teflon coating trays which prevent the resin from adhering.
Den fremkomne harpiks er lysegul til gui.The resulting resin is pale yellow to gui.
30 Det udviser f0lgende karakteristika: grænseviskositetstal η 0,17 dl/g I 28,0 mg KOH/g I0H 10,7 mg KOH/g 35 S (%) 1,43 (teoretisk 1,71)It exhibits the following characteristics: intrinsic viscosity η 0.17 dl / g I 28.0 mg KOH / g IOH 10.7 mg KOH / g 35 S (%) 1.43 (theoretical 1.71)
En vandig 20% oplpsning har et mælket udseende og er stabil ved henstand.An aqueous 20% solution has a milky appearance and is stable upon standing.
Eksempel 13Example 13
DK 156137BDK 156137B
20 I en reaktor anbringes: 5 isophtalsyre 232,4 g dimethylsu!fosucci nat (natriumsalt) 148,8 g diethylenglycol 233,2 g tetraisopropyl-o-titanat 0,6 ml 10Into a reactor are placed: 5 isophthalic acid 232.4 g dimethylsulfosuccinate (sodium salt) 148.8 g diethylene glycol 233.2 g tetraisopropyl o-titanate 0.6 ml
Arbejdsbetingelserne for kondensationsreaktionen er som angivet i eksempel 8.The working conditions of the condensation reaction are as given in Example 8.
Det fremkomne produkt udviser fplgende karakteristika: 15 IA 21,4 mg KOH/g I0H 9,7 mg KOH/gThe resulting product exhibits the following characteristics: 15 IA 21.4 mg KOH / g IOH 9.7 mg KOH / g
Mn 3250 g/mol S (%) 3,43 (teoretisk: 3,8) 20Mn 3250 g / mol S (%) 3.43 (theory: 3.8) 20
Overfladespænding 55,5 mN/m (i 1% vandig oplpsning ved 20°C).Surface tension 55.5 mN / m (in 1% aqueous solution at 20 ° C).
En vandig 30% oplosning af dette produkt er absolut vandklar. Grænseviskositetstallet ved koncentrationen 0,25% i opldsningen 25 phénol/tetrachlorethan er 0,9 dl/g.An aqueous 30% solution of this product is absolutely water clear. The intrinsic viscosity at the concentration of 0.25% in the solution of phenol / tetrachloroethane is 0.9 dl / g.
Eksempel 14 I en reaktor anbringes: 30 isophtalsyre 166 g dimethylsulfosuccinat (natriumsalt) 248 g diethylenglycol 233,2 g 35 tetraisopropyl-o-titanat 0,6 mlExample 14 Into a reactor: 30 isophthalic acid 166 g of dimethylsulfosuccinate (sodium salt) 248 g of diethylene glycol 233.2 g of tetraisopropyl o-titanate 0.6 ml
Arbejdsbetingelserne ved kondensationsreaktionen er som angivet i eksempel 8.The working conditions of the condensation reaction are as given in Example 8.
DK 156137 BDK 156137 B
2121
Den fremkomne harpiks er praktisk taget farvelds, skpr og af god stabilitet ved henstand.The resulting resin is practically farewell, crisp and of good stability upon standing.
Dets karakteristika er fplgende: 5 grænseviskositetstal η 0,095 dl/g IA 34,8 mg KOH/g I0H 22,8 mg KOH/gIts characteristics are as follows: 5 intrinsic viscosity η 0.095 dl / g IA 34.8 mg KOH / g IOH 22.8 mg KOH / g
Mn 1820 g/mol 10 S(%) 5,2 (teoretisk: 6,1)Mn 1820 g / mol 10 S (%) 5.2 (theory: 6.1)
Overfladespænding: 53*10_,3N/m (i 1% vandig oplpsning ved 20°C)Surface tension: 53 * 10_, 3N / m (in 1% aqueous solution at 20 ° C)
Der skal nu gennemgâs et eksempel pâ fremstilling af det sulfonerede 15 dérivât ud fra ethylenglycolmaleat, idet der ved sulfoneringen dannes di ethylenglycolsulfosucci nat.An example of preparation of the sulfonated derivative from ethylene glycol maleate is now to be considered, forming the ethylene glycol sulfosuccinate during the sulfonation.
I en kolbe forsynet med opvarmningsudstyr, propelomrprer, svaler og tildrypningstragt anbringes: 20 ethylenglycolmaleat 1 mol dvs. 292 g vand 368 gPlace in a flask equipped with heating equipment, propeller stirrer, swallower and drip funnel: 20 ethylene glycol maleate 1 mole ie. 292 g of water 368 g
Der opvarmes til 80°C.Heat to 80 ° C.
25 I tildrypningstragten, som er anbragt over kolben, anbringes: natriummetabisulfit 0,4 mol dvs. 76 g vand 100 g 30In the dropping funnel placed over the flask are placed: sodium metabisulphite 0.4 moles ie. 76 g water 100 g 30
Den fremkomne blanding sættes lidt efter lidt til kolben pâ en sâdan mâde, at temperaturen 80°C holdes. Denne tilsætning varer 25 minutter. For at opnâ en 50% oplpsning af sulfosuccinat tilsættes 268 g vand, og 90°C holdes i to timer.The resulting mixture is gradually added to the flask in such a way that the temperature is maintained at 80 ° C. This addition lasts 25 minutes. To obtain a 50% solution of sulfosuccinate, 268 g of water are added and 90 ° C is kept for two hours.
Den sâledes frembragte oplpsning tjener til fremstilling af en sulfoneret polyester i eksempel 15.The solution thus obtained serves to prepare a sulfonated polyester of Example 15.
35 I en reaktor anbringes:35 In a reactor is placed:
DK 156137 BDK 156137 B
Eksempel 15 22 5 isophtalsyre 166 g 50% oplpsning af diethylenglycol sulfosuccinat 736 g diethylenglycol 21,2 g tetraisopropyl-o-titanat 0,6 ml 10Example 15 22 isophthalic acid 166 g 50% solution of diethylene glycol sulfosuccinate 736 g diethylene glycol 21.2 g tetraisopropyl o-titanate 0.6 ml
En temperaturstigning under nitrogengennemstrpmning frembringes hurtigt indtil 100°C, derefter jævnt indtil 170°C, herefter destil-leres. Temperaturen hæves til 200°C. Kondensationen er herefter afsluttet; den totale varighed af kondensationsreaktionen er 5 15 timer.A temperature rise during nitrogen flow is rapidly produced up to 100 ° C, then evenly to 170 ° C, then distilled. The temperature is raised to 200 ° C. The condensation is then completed; the total duration of the condensation reaction is 5 hours.
Overskuddet af diethylenglycol afdestilleres straks ved trykket 2666 Pa i Ipbet af 3h time. Polyesteren er flydende ved 180-200°C. Det sâledes fremkomne sulfonerede produkt er orangerpdt, fast ved 20 normaltemperatur og oplpseligt i vand.The excess diethylene glycol is immediately distilled off at a pressure of 2666 Pa at the Ipbet of 3 hours. The polyester is liquid at 180-200 ° C. The sulfonated product thus obtained is orange-red, solid at normal temperature and soluble in water.
Eksempel 16 I en reaktor anbringes: 25 isophtalsyre 166 g 80% oplpsning af diethylenglycol sulfosuccinat 117 g diethylenglycol 90 g 30 tetraisopropyl-o-titanat 0,6 mlExample 16 Place in a reactor: 25 isophthalic acid 166 g 80% solution of diethylene glycol sulfosuccinate 117 g diethylene glycol 90 g 30 tetraisopropyl o-titanate 0.6 ml
Der arbejdes under betingelser som angivet i eksempel 15. Der fâs et produkt, som ligner det foregâende, men er en smule mere hygrosko-pisk.Work is done under conditions as in Example 15. There is a product which is similar to the preceding but is slightly more hygroscopic.
3535
Disse polyestre er ligeledes blevet gennemprdvet som slettemidler under de allerede beskrevne omstændigheder.These polyesters have also been proven to be deletion agents in the circumstances already described.
Med de tre bade, som er benyttet til behandlingen af kædegarn afWith the three baths used for the treatment of warp yarn
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2323
Tergal®, er der ikke blevet konstateret afsætninger af slettemiddel pâ vævekammen efter 50 meter.Tergal®, no erosion deposits have been found on the loom after 50 meters.
Ved sletning af en trâd af celluloseacetat i et bad, som indeholder 5 4% tprstof (vægtbasis) bestâende af produktet fra eksempel 11, er der iagttaget en "vævningsevne", som er helt korrekt.By deleting a strand of cellulose acetate in a bath containing 5% by weight of the fabric (weight basis) consisting of the product of Example 11, a "weaving ability" is observed which is quite correct.
Ud over anvendelser inden for tekstilomrâdet skal nævnes den mulige udnyttelse af disse vandoplpselige, sulfonerede polyestre, uanset 10 deres fremstillingsmâde, som thermofdlsomme klæbestoffer, der kan dispergeres i vand; en anvendelsesform som er specielt egnet inden for omràdet med papir og plastfolier (cellofan, mylar). De kan endvidere anvendes som emballage i form af vandoplpselige, folie-beholdere, der bâde kan indeholde fast stof og væsker.In addition to applications in the field of textiles, mention should be made of the possible utilization of these water-soluble, sulfonated polyesters, regardless of their mode of manufacture, as thermoplastic adhesives which can be dispersed in water; an application which is particularly suitable in the field of paper and plastic films (cellophane, mylar). They can also be used as packaging in the form of water-soluble foil containers which can both contain solids and liquids.
15 20 25 30 3515 20 25 30 35
Claims (2)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7226094 | 1972-07-13 | ||
| FR7226094A FR2192133B1 (en) | 1972-07-13 | 1972-07-13 | |
| FR7301358 | 1973-01-10 | ||
| FR7301358A FR2213302B2 (en) | 1972-07-13 | 1973-01-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DK156137B true DK156137B (en) | 1989-06-26 |
| DK156137C DK156137C (en) | 1989-11-06 |
Family
ID=26217223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK387273A DK156137C (en) | 1972-07-13 | 1973-07-12 | PROCEDURE FOR THE PREPARATION OF WATER SOLUBLE, SULPHONATED POLYESTERS |
Country Status (12)
| Country | Link |
|---|---|
| JP (2) | JPS5617369B2 (en) |
| AR (1) | AR199482A1 (en) |
| BE (1) | BE802275A (en) |
| CH (3) | CH567048A5 (en) |
| DE (1) | DE2335480C2 (en) |
| DK (1) | DK156137C (en) |
| ES (1) | ES416819A1 (en) |
| FR (2) | FR2192133B1 (en) |
| GB (1) | GB1418975A (en) |
| IT (1) | IT996077B (en) |
| NL (1) | NL174649C (en) |
| SE (2) | SE415840B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4048149A (en) * | 1972-07-13 | 1977-09-13 | Rhone-Poulenc Industries | Water-soluble sulfonated polyesters |
| JPS557865A (en) * | 1978-07-05 | 1980-01-21 | Toray Ind Inc | Preparation of aqueous solution of polyester copolymer |
| JPS61245377A (en) * | 1985-04-18 | 1986-10-31 | 東洋紡績株式会社 | Fiber product having fire retardance |
| US5281630A (en) * | 1991-12-18 | 1994-01-25 | The Seydel Companies | Sulfonated water-soluble or water-dispersible polyester resin compositions |
| FR2728915B1 (en) * | 1994-12-30 | 1997-01-31 | Rhone Poulenc Chimie | SULPHONATED COPOLYESTERS WITH POLYORGANOSILOXANE PATTERNS AS TEXTILE SIZING AGENTS AND METHOD FOR SIZING TEXTILE YARNS OR FIBERS USING THE SAME |
| US6166165A (en) * | 1996-12-18 | 2000-12-26 | Witco Corporation | Polyurethane synthesis from functional group terminated polymers containing sulfonate groups |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1816163A1 (en) * | 1968-01-03 | 1969-07-31 | Eastman Kodak Co | Linear polyesters dispersible in water |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2028091A (en) * | 1933-07-28 | 1936-01-14 | American Cyanamid & Chem Corp | Esters of sulphodicarboxylic acids |
-
1972
- 1972-07-13 FR FR7226094A patent/FR2192133B1/fr not_active Expired
-
1973
- 1973-01-10 FR FR7301358A patent/FR2213302B2/fr not_active Expired
- 1973-05-30 GB GB2572873A patent/GB1418975A/en not_active Expired
- 1973-06-13 AR AR24854473A patent/AR199482A1/en active
- 1973-06-22 NL NL7308751A patent/NL174649C/en not_active IP Right Cessation
- 1973-06-28 IT IT5109573A patent/IT996077B/en active
- 1973-07-03 CH CH968573A patent/CH567048A5/xx not_active IP Right Cessation
- 1973-07-03 CH CH1386673*A patent/CH577057B5/xx not_active IP Right Cessation
- 1973-07-03 CH CH1386673D patent/CH1386673A4/xx unknown
- 1973-07-09 SE SE7309605A patent/SE415840B/en unknown
- 1973-07-11 JP JP7822873A patent/JPS5617369B2/ja not_active Expired
- 1973-07-12 DE DE19732335480 patent/DE2335480C2/en not_active Expired
- 1973-07-12 BE BE133420A patent/BE802275A/en not_active IP Right Cessation
- 1973-07-12 DK DK387273A patent/DK156137C/en not_active IP Right Cessation
- 1973-07-12 ES ES416819A patent/ES416819A1/en not_active Expired
-
1975
- 1975-05-14 JP JP5715175A patent/JPS5318638B2/ja not_active Expired
-
1977
- 1977-04-14 SE SE7704274A patent/SE421807B/en not_active IP Right Cessation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1816163A1 (en) * | 1968-01-03 | 1969-07-31 | Eastman Kodak Co | Linear polyesters dispersible in water |
Also Published As
| Publication number | Publication date |
|---|---|
| CH1386673A4 (en) | 1975-10-31 |
| FR2213302B2 (en) | 1976-11-05 |
| DE2335480C2 (en) | 1982-02-04 |
| NL174649C (en) | 1984-07-16 |
| DK156137C (en) | 1989-11-06 |
| DE2335480A1 (en) | 1974-01-31 |
| JPS50157691A (en) | 1975-12-19 |
| JPS5318638B2 (en) | 1978-06-16 |
| NL7308751A (en) | 1974-01-15 |
| CH567048A5 (en) | 1975-09-30 |
| CH577057B5 (en) | 1976-06-30 |
| GB1418975A (en) | 1975-12-24 |
| FR2213302A2 (en) | 1974-08-02 |
| ES416819A1 (en) | 1976-02-16 |
| FR2192133A1 (en) | 1974-02-08 |
| SE415840B (en) | 1980-11-03 |
| BE802275A (en) | 1974-01-14 |
| SE7704274L (en) | 1977-04-14 |
| IT996077B (en) | 1975-12-10 |
| AR199482A1 (en) | 1974-09-09 |
| NL174649B (en) | 1984-02-16 |
| SE421807B (en) | 1982-02-01 |
| JPS4959195A (en) | 1974-06-08 |
| FR2192133B1 (en) | 1974-10-25 |
| JPS5617369B2 (en) | 1981-04-22 |
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| PBP | Patent lapsed |