CN1293266A - Technique for regenerating ceratin fibres - Google Patents

Abstract

A process for preparing regenerated azelon from ceratin with various animal hairs including leftover wool, pig britlet, fowls' feather and ox hair, waste silk and waste leather includes such steps as collecting raw material, defatting, removing impurities, dissolving, cross linking protein, enclosing free aminos, preparing the spinning ceratin liquid, and spinning to obtain the regenerated azelon.

Description

The technology of regenerating ceratin fibres

The invention belongs to the technology of a kind of protein renaturation utilization of macromolecular material and engineering Application Areas.Be from the keratin raw material, to extract albumen, invent manufacture method into the protein renaturation fiber.

The leftover bits and pieces raw material number that the annual wool industry in the whole nation produces is in ten thousand tons, and common feature of toe feathering (mainly being wool) is that average fiber length is short, the discrete length degree is big under these, generally falls as waste disposal in the past.In addition, a large amount of poultry hair (for example pig hair) is because quality is thick and stiff, and fiber is short, can not be directly for weaving usefulness, and the past all is used as fertilizer.These raw materials are fully used, and several generations are inquiring into the protein renaturation fiber always, but never have breakthrough progress.

The chemical nature of all kinds of animal wools all is a keratin, and they all are the macromolecules that several amino acids links and forms with peptide bond.Purpose of the present invention is therefrom extracted protein and is made spinning solution after being exactly the special chemical treatment of various keratin (as pig hair, waste wool, ox hair, waste leather etc.) process that can not spin, and regeneration can spin pure protein or the albumen blended fiber that can knit.For the novel artificial fibre of a class is made in China's chemical fibre industry.

Typical process flow of the present invention: the crosslinked → sealing free amine group → albumen spinning solution → spinning → protein renaturation fiber of raw material → degreasing impurity elimination → dissolving → protein.

Below technology of the present invention is described in further detail: 1, degreasing impurity elimination:

The method of decontamination is to beat with the unhairing machine comb, uses the clear water rinsing.

The method of degreasing: 1. add suitable surfactant washing with warm water, use the clear water rinsing again, then drying for standby.2. can soak or the kiering degreasing with the Na2S hot solution.2, dissolving: the process of animal wool dissolving mainly is exactly to untie disulfide bond, and cutin fiber is dispersed into keratin molecule.Process conditions are;

Concentration of lye: NaOH 30-50g/l

Bath raio: 1: 3-1: 5

Temperature: feed temperature 80-85 ℃, can not surpass 90 ℃, solution temperature 60-70 ℃.

Time: 60-90 minute, decide on the dissolving situation, generally be controlled at dissolving about 90%.

Lysate need pass through twice (or multiple tracks filtration), and the elimination solid matter forms transparent protein liquid.3, protein is crosslinked:

Protein crosslinked has two kinds of methods:

A, make crosslinking agent with epoxychloropropane:

Epoxychloropropane (owf) 1-3%

Temperature 40-50 ℃

PH 10-11

Time 1.5-2.5 hour

B, make crosslinking agent with formaldehyde:

Formaldehyde (owf) 1-2.5%

Temperature 40-50 ℃

PH 7．5-8．5

Time 1.5-2.5 hours 4, sealing free amine group:

Method A: acrylonitrile (owf) 2%-3%

50 ℃ of temperature

About 1 hour time

Method B: formaldehyde (owf) 1-3%

Temperature 60-70 ℃

About 1 hour time 5, albumen spinning solution: spinning solution is condensed into thick liquid (choose a bit with glass rod, drip into wire) and gets final product spinning.Also can about 50 ℃, place maturation 24-36 hour again.Concrete grammar is looked the difference of product and is selected.6, spinning: can be divided into pure protein spinning and blend spinning by the raw material branch.Can be divided into long filament and short fiber by product.Be illustrated with several typical process routes at this.

A, pure protein spinning:

By carrying out spinning through the crosslinking protein spinning solution:

Coagulating bath: H ₂SO ₄70-100g/l

Na ₂SO ₄ 350-370g／l

ZnSO ₄ 20-30g／l

Or use

Al ₂(SO ₄) ₃ 350-450g／l

H ₂SO ₄ 20-30g／l

Or use

MgSO ₄ 330-380g／l

H ₂SO ₄ 20-30g／l

Or use

MgSO ₄ 330-380g／l

H ₂SO ₄ 60-90g／l

Temperature: 35-45 ℃

Spin speed: 5-6 rice/minute

Operations such as spun silk need are stretched, humid heat treatment, cured, washing and drying become finished product.

B, the spinning of keratin vinylon fiber

A. preparation of spinning solution:

Use H ₂SO ₄In and protein dissolution liquid to PH be about 4, be settled out faint yellow resilient albumen, wash, and smash to pieces, soak.

Clean polyvinyl alcohol, heating for dissolving to solution transparent till.

Under agitation transfer PH=12, add 1-2% (owf) ammonium persulfate, progressively add the protein of smashing to pieces, keep about PH11 with NaOH, about 20-30 minute, slowly be cooled to 85 ℃, about 1 hour, protein dissolution finished.

When PH9-11, make crosslinking agent with formaldehyde, under stirring condition, slowly drip and make a large amount of protein molecules and polyvinyl alcohol crosslinked.Make spinning solution.

B. maturation, filtration, concentrate: under 65-70 ℃ of constant temperature maturation 10-12 hour, filter.Stir concentrated at 90 ℃.

C. coagulating bath: saturated sodium sulphate proportion 1.28-1.30

H ₂SO ₄ 40g／l

45 ℃ of temperature

Stretch bath: saturated sodium sulphate proportion 1.32

95 ℃ of temperature

Draw ratio: 5 times

C, protein cellulose viscose spinning

Mix with protein liquid after crosslinked and viscose glue stoste, make albumen rayon spinning liquid.Viscosity 120 ± 10 seconds, degree of ripeness 12 ± 1.

Coagulating bath: H ₂SO ₄35-40g/l

Na ₂SO ₄ 260±20g／l

ZnSO ₄ 10g／l

Temperature: 40-50 ℃

Soak length: 50 centimetres

Become finished product after the postprocessing working procedures such as the fiber drawn after the spinning, washing, acetalation, desulfurization, washing, last oil drying.

Claims (4)

1, a kind of extraction albumen, the method for manufacturing protein renaturation silk, the typical method of regeneration albumen silk comprises the crosslinked → sealing free amine group → albumen spinning solution → spinning → protein renaturation fiber of raw material → degreasing impurity elimination → dissolving → protein.It is characterized in that with various protein raw materials such as various animal wools (comprising woollen mill all kinds of toe feathering, pig hair, ox hair, chicken feather, drake feathers etc. down), useless silk, waste leathers as the azelon raw material.

2, the method for claim 1, the crosslinked operation of wherein said protein has following method respectively:

A, make crosslinking agent with epoxychloropropane:

Epoxychloropropane (owf) 1-3%

Temperature 40-50 ℃

PH 10-11

Time 1.5-2.5 hour

B, make crosslinking agent with formaldehyde:

Formaldehyde (owf) 1-2.5%

Temperature 40-50 ℃

PH 7．5-8．5

Time 1.5-2.5 hour

3, the method for claim 1, wherein said sealing free amine group operation can be selected from following operation:

A: acrylonitrile (owf) 2%-3%

50 ℃ of temperature

About 1 hour time

B: formaldehyde (owf) 1-3%

Temperature 60-70 ℃

About 1 hour time

4, the method for claim 1, wherein said spinning process has following several method respectively:

A, pure protein spinning:

By carrying out spinning through the crosslinking protein spinning solution:

Coagulating bath: H ₂SO ₄70-100g/l

Na ₂SO ₄ 350-370g／l

ZnSO ₄ 20-30g／l

Or use

Al ₂(SO ₄) ₃ 350-450g／l

H ₂SO ₄ 20-30g／l

Or use

MgSO ₄ 330-380g／l

H ₂SO ₄ 60-90g／l

Temperature: 35-45 ℃

Spin speed: 5-6 rice/minute

Operations such as spun silk need are stretched, humid heat treatment, cured, washing and drying become finished product.

B, the spinning of keratin vinylon fiber

A. preparation of spinning solution:

Use H ₂SO ₄In and protein dissolution liquid to PH be about 4, be settled out faint yellow resilient albumen, wash, and smash to pieces, soak.

Clean polyvinyl alcohol, heating for dissolving to solution transparent till.

Under agitation transfer PH=12, add 1-2% (owf) ammonium persulfate, progressively add the protein of smashing to pieces, keep about PH11 with NaOH, about 20-30 minute, slowly be cooled to 85 ℃, about 1 hour, protein dissolution finished.

When PH9-11, make crosslinking agent with formaldehyde, under stirring condition, slowly drip and make a large amount of protein molecules and polyvinyl alcohol crosslinked.Make spinning solution.

B. maturation, filtration, concentrate: under 65-70 ℃ of constant temperature maturation 10-12 hour, filter.Stir concentrated at 90 ℃.

C. coagulating bath: saturated sodium sulphate proportion 1.28-1.30

H ₂SO ₄ 40g／1

45 ℃ of temperature

Stretch bath: saturated sodium sulphate proportion 1.32

95 ℃ of temperature

Draw ratio: 5 times

C, protein cellulose viscose spinning

Mix with protein liquid after crosslinked and viscose glue stoste, make albumen rayon spinning liquid.Viscosity 120 ± 10 seconds, degree of ripeness 12 ± 1.

Coagulating bath: H ₂SO ₄35-40g/l

Na ₂SO ₄ 260±20g／l

ZnSO ₄ 10g／l

Temperature: 40-50 ℃

Soak length: 50 centimetres

Become finished product after the postprocessing working procedures such as the fiber drawn after the spinning, washing, acetalation, desulfurization, washing, last oil drying.