US3492079A - Acetalisation of polyvinyl alcohol yarns - Google Patents

Acetalisation of polyvinyl alcohol yarns Download PDF

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Publication number
US3492079A
US3492079A US448992A US3492079DA US3492079A US 3492079 A US3492079 A US 3492079A US 448992 A US448992 A US 448992A US 3492079D A US3492079D A US 3492079DA US 3492079 A US3492079 A US 3492079A
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United States
Prior art keywords
yarn
acetalisation
yarns
bath
polyvinyl alcohol
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Expired - Lifetime
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US448992A
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English (en)
Inventor
Paul Couchoud
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Rhodiaceta SA
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Rhodiaceta SA
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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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/12—Aldehydes; Ketones
    • D06M13/127—Mono-aldehydes, e.g. formaldehyde; Monoketones

Definitions

  • This invention relates to the continuous formalisation of polyvinyl alcohol yarns.
  • yarns By yarns is to be understood a group of filaments obtained by wet or dry spinning or by spinning in the semi-molten state, which group may be fairly small when continuous filament yarns are concerned, or fairly large or large when it is a question of high-denier tows which are later to be cut or broken to obtain staple fibres.
  • polyvinyl alcohol is used for manufacturing yarns having interesting textile properties by spinning aqueous solutions thereof, hot drawing the filaments so formed, and then acetalising them.
  • the acetalisation treatment is carried out in an acid medium by means of an aldehyde, for example formaldehyde, acetaldehyde or benzaldehyde.
  • the aldehyde reacts with a certain number of the hydroxyl groups to form acetal groups, and the greater the degree of acetalisation, the greater is the reduction in the solubility in water of the yarn and in consequence its shrinkage in boiling water.
  • the acetalisation of polyvinyl alcohol is easier when the filaments obtained from the initial aqueous solution have not been dried or have been incompletely dried and have not undergone any thermal treatment, particularly hot drawing.
  • the acetalisation reaction is instantaneous when the filaments, after their formation from an aqueous solution of polyvinyl alcohol, are treated with a solution of formaldehyde and hydrochloric acid, either immediately or after more or less complete drying, but without any intermediate thermal treatment such as a hot drawing.
  • the filaments are very much changed by this acetalisation, in that they swell and shrink strongly in the treatment bath, and this is particularly serious in low denier yarns which tend to lose their textile qualities.
  • the acetalisation is generally carried out in U-shaped tubes, the yarn being delivered by one of the branches of the tube and remaining in bulk in the bottom of the U before being taken up again at the outlet of the other branch.
  • Such an arrangement which can be very easily employed for tows having a large number of filaments, cannot be used in practice for low denier yarns, because there are then produced numerous tangles and knots in the bottom of the U-tube, preventing the successful use of the process and impairing the quality of the yarn obtained. It was therefore necessary to find a faster acetalisation process which can be carried out continuously on a yarn which is normally resistant to acetalisation reagents when held under tension.
  • the yarn thus obtained can be inpregnated by continuous passage, optionally under tension, in an acetalisation bath, and the reaction terminated by a thermal treatment on spools; however, such a treatment is only semi-continuous, and the total duration of the reaction is never shorter than 6 minutes, at least one minute of continuous treatment and at least 5 minutes of discontinuous treatment.
  • the present invention comprises a process for the continuous formalisation of drawn polyvinyl alcohol yarns, in which the yarns are caused to travel for less than 3 minutes under tension through a bath at a temperature of 90 C., containing 50 to 60% by weight of Water, and sulphuric acid and formaldehyde in proportions represented by points Within a substantially prismatoidal volume defined by the following points:
  • the tension applied to the filaments during the acetali sation should be higher than 0.25 g./tex, but must obviously be below the breaking tension of the yarn being treated, and is preferably below 1.25 g./tex.
  • the ratio between sulphuric acid and formaldehyde in the formalisation bath can with advantage be as close as possible to the equimolec-ular ratio, that is to say, 3.26
  • the quantity of water in the treatment bath is between 50 and 60% and preferably as close as pos- Sible to 57%. If smaller or larger quantities of water are used distinctly longer reaction times are necessary, making continuous working difficult.
  • the process of the invention has the great advantage of permitting a reaction time very much shorter than 3 minutes and generally shorter than 30 seconds, e.g. 6 to 20 seconds, so making a continuous treat- -ment thoroughly practicable.
  • the reaction time is moreover shorter when the yarn has been washed with water or with an aqueous solution of a Wetting agent and dried before the treatment.
  • Such a process thus presents a very great economic advantage. It is applicable equally well to continuous yarns of low denier and to tows of high denier, although it is known that the former are normally much more difficult to acetalise; this is likewise a great advantage of the new process by comparison with those previously used.
  • the process can be used with any equipment suitable for the continuous treatment of yarns under tension with acid-reacting liquids. Its great speed removes the need for particular equipment.
  • FIGURE 1 is a graph showing, for a composition with 50% of water, the surface A, B, C, D, E within which all points correspond to contents of sulphuric acid and formaldehyde suitable for carrying out the new process,
  • FIGURE 2 is a similar graph showing, for a composition with 57% of Water, the corresponding surface A B1 C1: D1! E15 and FIGURE 3 is a similar graph showing, for a composition with 60% of water, the corresponding surface A B2, C2: D2: E2-
  • EXAMPLE 1 A 40 filament polyvinyl alcohol yarn is oiled by means of polyethylene glycol, drawn to 5 times its initial length on a heating element and then shrunk by 15% at 230 C.; it then has a count of 80 decitex. The yarn so obtained is passed through a bath at 85 C. containing:
  • the yarn is then washed and dried without tension.
  • the yarn so obtained contains 11% of combined formaldehyde, corresponding to a degree of formalisation of 33%; when immersed in boiling water for 5 minutes it shrinks by 3 4 EXAMPLE 2 EXAMPLE 3 A yarn, identical with that of Example 1 after shrinkage, is passed through a bath at 82 C. containing:
  • the yarn so obtained after being washed and dried without tension, shrinks by only 3% when immersed in boiling Water for 5 minutes.
  • EXAMPLE 4' A yarn, identical to that of Example 1 after shrinking, is passed through a bath at 89 C. containing:
  • the yarn after being washed and then dried without tension, shrinks by 2% on immersion for 5 minutes in boiling water.
  • EXAMPLE 5 A yarn, identical to that of Example 1 after shrinking, is Washed in an aqueous solution containing 2% of a wetting agent consisting of a condensate of ethylene oxide and lauryl alcohol and dried, after which it is treated in a bath at C. containing:
  • EXAMPLE 6 A yarn, identical with that of Example 1 after shrinking, is treated in a bath at 85 C. containing:
  • the residence time is 10 seconds, and the tension is 3 g.
  • the yarn after being washed and dried without tension, does not shrink when immersed for 5 minutes in boiling water.
  • EXAMPLE 7 l A yarn, identical to that of Example 1 after shrinking, is washed in an aqueous solution containing 2% of the wetting agent used in Example 5 and dried, after which it is treated in a bath at 85 C. containing:
  • the yarn travels continuously through this bath under a tension of 3 g., the residence time being 8 seconds.
  • the yarn after washing and drying, shrinks by 4% on immersion for 5 minutes in boiling water.
  • a process for the continuous formalisation of yarns of polyvinyl alcohol which have already been drawn at an elevated temperature in which the yarns are caused to travel under a tension between 0.25 and 1.25 g./tex for less than 3 minutes through a bath at a temperature of 80 to 90 C. containing 50 to 60% by weight of water, and sulphuric acid and formaldehyde in proportions represented by points within a substantiall prismatoidal volume defined by the shaded areas of the graphs of FIGURES 1-3, the complement of 100% being formed by sodium sulphate.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Artificial Filaments (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
US448992A 1964-04-22 1965-04-19 Acetalisation of polyvinyl alcohol yarns Expired - Lifetime US3492079A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR971879A FR1401375A (fr) 1964-04-22 1964-04-22 Procédé pour l'acétalisation de fils à base d'alcool polyvinylique

Publications (1)

Publication Number Publication Date
US3492079A true US3492079A (en) 1970-01-27

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Application Number Title Priority Date Filing Date
US448992A Expired - Lifetime US3492079A (en) 1964-04-22 1965-04-19 Acetalisation of polyvinyl alcohol yarns

Country Status (8)

Country Link
US (1) US3492079A (fr)
BE (1) BE662826A (fr)
CH (1) CH468507A (fr)
DE (1) DE1494739A1 (fr)
ES (1) ES312131A1 (fr)
FR (1) FR1401375A (fr)
GB (1) GB1064359A (fr)
NL (1) NL6505049A (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050118419A1 (en) * 2003-11-27 2005-06-02 Hyosung Corporation Crosslinked polyvinyl alcohol fiber and method for producing the same

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2890927A (en) * 1958-01-24 1959-06-16 Mitsubishi Rayon Co Production of fibers made of or containing polyvinyl alcohol
FR1199296A (fr) * 1957-01-16 1959-12-11 Hoechst Ag Procédé de préparation de fils d'alcool polyvinylique stables à chaud
US2960384A (en) * 1951-12-17 1960-11-15 Kurashiki Rayon Co Method of improving the mechanical and dyeing properties of shaped polyvinyl alcohol structures
US2977183A (en) * 1951-12-19 1961-03-28 Air Reduction Process of improving the dyeing properties of polyvinyl alcohol fibers
US2992204A (en) * 1956-03-30 1961-07-11 Air Reduction Polyvinyl alcohol filaments of improved dye affinity
GB879193A (en) * 1957-07-19 1961-10-04 Hoechst Ag Manufacture of polyvinyl alcohol fibres
US3011861A (en) * 1959-03-26 1961-12-05 Kurashiki Rayon Co Wet spinning polyvinyl alcohol process
US3027224A (en) * 1958-12-31 1962-03-27 Air Reduction Polyvinyl alcohol fibers having improved elasticity
US3066999A (en) * 1958-08-19 1962-12-04 Kurashiki Rayon Co Polyvinyl alcohol fiber and method of making the same
US3105058A (en) * 1957-06-17 1963-09-24 Kurashiki Rayon Co Shaped articles of polyvinyl alcohol polymer blends
US3124415A (en) * 1964-03-10 hours
US3137540A (en) * 1952-03-12 1964-06-16 Kurashiki Rayon Co Treatment of shaped polyvinyl alcohol bodies
US3167604A (en) * 1959-04-13 1965-01-26 Kanegafuchi Spinning Co Ltd Process for the production of fibrous products consisting of polyvinyl alcohol or its derivatives

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3124415A (en) * 1964-03-10 hours
US2960384A (en) * 1951-12-17 1960-11-15 Kurashiki Rayon Co Method of improving the mechanical and dyeing properties of shaped polyvinyl alcohol structures
US2977183A (en) * 1951-12-19 1961-03-28 Air Reduction Process of improving the dyeing properties of polyvinyl alcohol fibers
US3137540A (en) * 1952-03-12 1964-06-16 Kurashiki Rayon Co Treatment of shaped polyvinyl alcohol bodies
US2992204A (en) * 1956-03-30 1961-07-11 Air Reduction Polyvinyl alcohol filaments of improved dye affinity
FR1199296A (fr) * 1957-01-16 1959-12-11 Hoechst Ag Procédé de préparation de fils d'alcool polyvinylique stables à chaud
US3105058A (en) * 1957-06-17 1963-09-24 Kurashiki Rayon Co Shaped articles of polyvinyl alcohol polymer blends
GB879193A (en) * 1957-07-19 1961-10-04 Hoechst Ag Manufacture of polyvinyl alcohol fibres
US2890927A (en) * 1958-01-24 1959-06-16 Mitsubishi Rayon Co Production of fibers made of or containing polyvinyl alcohol
US3066999A (en) * 1958-08-19 1962-12-04 Kurashiki Rayon Co Polyvinyl alcohol fiber and method of making the same
US3027224A (en) * 1958-12-31 1962-03-27 Air Reduction Polyvinyl alcohol fibers having improved elasticity
US3011861A (en) * 1959-03-26 1961-12-05 Kurashiki Rayon Co Wet spinning polyvinyl alcohol process
US3167604A (en) * 1959-04-13 1965-01-26 Kanegafuchi Spinning Co Ltd Process for the production of fibrous products consisting of polyvinyl alcohol or its derivatives

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050118419A1 (en) * 2003-11-27 2005-06-02 Hyosung Corporation Crosslinked polyvinyl alcohol fiber and method for producing the same

Also Published As

Publication number Publication date
DE1494739A1 (de) 1969-12-11
NL6505049A (fr) 1965-10-25
BE662826A (fr) 1965-10-21
GB1064359A (en) 1967-04-05
ES312131A1 (es) 1965-10-01
CH468507A (fr) 1968-10-31
FR1401375A (fr) 1965-06-04

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