CN107090607A - A kind of preparation method of PVA/ cellulose composite fibers - Google Patents
A kind of preparation method of PVA/ cellulose composite fibers Download PDFInfo
- Publication number
- CN107090607A CN107090607A CN201710384820.9A CN201710384820A CN107090607A CN 107090607 A CN107090607 A CN 107090607A CN 201710384820 A CN201710384820 A CN 201710384820A CN 107090607 A CN107090607 A CN 107090607A
- Authority
- CN
- China
- Prior art keywords
- pva
- preparation
- composite fibers
- cellulose composite
- bath
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 80
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 51
- 229920002678 cellulose Polymers 0.000 title claims abstract description 48
- 239000001913 cellulose Substances 0.000 title claims abstract description 47
- 238000009987 spinning Methods 0.000 claims abstract description 60
- 238000004132 cross linking Methods 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 36
- 238000007493 shaping process Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 238000000465 moulding Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 95
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 95
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 34
- 229920000297 Rayon Polymers 0.000 claims description 31
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 26
- 230000001112 coagulating effect Effects 0.000 claims description 20
- 238000012545 processing Methods 0.000 claims description 18
- 239000003292 glue Substances 0.000 claims description 16
- 239000006210 lotion Substances 0.000 claims description 14
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 13
- 235000011152 sodium sulphate Nutrition 0.000 claims description 13
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 238000007711 solidification Methods 0.000 claims description 9
- 230000008023 solidification Effects 0.000 claims description 9
- 238000006477 desulfuration reaction Methods 0.000 claims description 8
- 230000023556 desulfurization Effects 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 238000004061 bleaching Methods 0.000 claims description 7
- 230000015271 coagulation Effects 0.000 claims description 7
- 238000005345 coagulation Methods 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 7
- 229960001763 zinc sulfate Drugs 0.000 claims description 7
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 7
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 5
- 235000010265 sodium sulphite Nutrition 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims 13
- 229940068984 polyvinyl alcohol Drugs 0.000 claims 3
- 239000004753 textile Substances 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000013589 supplement Substances 0.000 abstract 1
- 235000010980 cellulose Nutrition 0.000 description 35
- 230000006378 damage Effects 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 230000008569 process Effects 0.000 description 11
- 239000002253 acid Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229920002978 Vinylon Polymers 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
- D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
- D02J1/224—Selection or control of the temperature during stretching
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J13/00—Heating or cooling the yarn, thread, cord, rope, or the like, not specific to any one of the processes provided for in this subclass
-
- 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
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/003—Treatment with radio-waves or microwaves
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
- Multicomponent Fibers (AREA)
Abstract
The present invention provides a kind of preparation method of PVA/ cellulose composite fibers, the preparation method, including the spinning solution preparation process, spinning moulding step, damp and hot stretching step, tow process step, tow drying steps, xeothermic stretching step, heat treatment shaping step, simple cross-linking step.The present invention omits PVA solution precrosslink and further crosslinking bath；PVA/ cellulose composite fibers are prepared, can not only make two kinds of component mutual supplement with each other's advantages, and both blending in structure, dry strong >=2.12cN/dtex of the PVA/ cellulose composite fibers of preparation, wet strong >=1.08cN/dtex can be realized；Composite fibre water resistance prepared by the present invention is high, and textile processibility is good, and hydroscopicity is 7.6~12.0%.
Description
Technical field
The present invention relates to a kind of preparation method of polyvinyl alcohol (PVA)/cellulose composite fiber, specifically, it is related to one
It is that raw material carries out two-component to plant with cellulose pulp and polyvinyl alcohol (PVA)（PVA+ celluloses）The preparation method of composite fibre,
Belong to textile technology field.
Background technology
There is two or more immiscible polymer fiber on same fibre section, this fiber claims multiple
Condensating fiber, it is the physical modification fiber grown up 1960s.It can obtain simultaneous using composite fibre manufacturing technology
There is the bicomponent fibre of two kinds of polymer characteristic.
Cellulosic fibre is mainly viscose rayon, due to good hygroscopicity, comfortable and easy to wear, and spinnability is excellent, is widely used,
It is mainly prepared by wet spinning.Polyvinyl is the trade name of vinylon, its performance close to cotton,
There is the title of " synthesis cotton ", be the kind of hygroscopicity maximum in existing synthetic fibers.Vinal (PVA fibers) is a kind of
Of great value functional differential fibers, its intensity is high, degree of stretching is low, modulus is big, acid and alkali-resistance, weather resisteant and good hygroscopicity, resistance to
Burn into, which is not afraid of, damages by worms, and the Exposure to Sunlight of long period is little to its intensity effect.
PVA/ cellulose composite fibers, the characteristics of having viscose rayon and PVA fibers concurrently, are provided newly for the exploitation of composite fibre
Idea and method, with preferable development prospect.
Patent CN102851774A disclose it is a kind of improve viscose fiber strength method, this method be using viscose rayon as
Matrix, polyvinyl alcohol is reinforcing material, for the purpose of the intensity for improving viscose rayon, but the preparation method is fully according to viscose glue
Method preparation technology, exist PVA shaping it is insufficient, spinning speed is slow（Its spinning speed is 10-30m/min）, follow-up crosslinking time
The problems such as length, low production efficiency, it is unfavorable in industrialization production, and cross-linking process using formaldehyde, adds the harm to human body
And environmental pollution.
Patent ZL201310085220.4 discloses a kind of preparation side of PVA composite high-strengths high modulus fibre cellulose fiber
Method, this method is to carry out the PVA solution of precrosslink and viscose glue dope blending according to viscose rayon preparation technology, adds crosslinking
Number of times（Totally three times）, production process is various, and production efficiency is low.
Technical problem present in prior art：
（1）In the prior art in order to increase the intensity and modulus of PVA/ cellulose composite fibers, multiple crosslinking Treatment is typically taken,
Precrosslink including PVA solution, the two further cross mouldings of bath of spinning blended liquid, continuation crosslinking bath in post processing etc.；
But PVA solution precrosslink is not easily controlled crosslinking degree, PVA water-soluble decline is caused, and influences follow-up co-blended spinning
The strainability of liquid；
The aldehyde materials such as the acetaldehyde that further crosslinking bath is used have larger penetrating odor, cause production environment to deteriorate, dirty
Environment is contaminated, and cross-linking effect is not obvious.
（2）Prior art reduces the number of times of crosslinking, and the intensity and modulus of PVA/ cellulose composite fibers can be greatly reduced, and
And the water resistance of composite fibre can be reduced.
The content of the invention
The problem to be solved in the present invention is that there is provided a kind of preparation side of PVA/ cellulose composite fibers for deficiency above
Method, technique is simple, using cellulose pulp and polyvinyl alcohol as raw material, by adjusting shaping bath composition, makes both while being molded
To composite fibre filament.Compound tow carries out tow processing after damp and hot stretching, then through xeothermic stretching and heat treatment shaping,
After simple crosslinking, then through processes such as supercooling, cut-outs, composite cellulose fiber is made.
The present invention goal of the invention be：
（1）A kind of preparation method of new PVA/ cellulose composite fibers is provided, the art of this patent is in viscose rayon and polyvinyl
Innovated on the basis of the moulding process of fiber, achieve preferable effect.
（2）For prior art, PVA solution precrosslink and further crosslinking bath are omitted, in the situation of crosslinking number of times reduction
Under, the intensity and wet modulus of PVA/ cellulose composite fibers are not varied widely, and are improved water resistance, are improved simultaneously
Follow-up spinning effect and working environment, improve spinning efficiency, and assign fiber preferable performance.
To solve above technical problem, the technical solution adopted by the present invention is as follows：
A kind of preparation method of PVA/ cellulose composite fibers, including it is the spinning solution preparation process, spinning moulding step, wet
Hot-stretch step, tow process step, tow drying steps, xeothermic stretching step, heat treatment shaping step, simple crosslinking step
Suddenly.
The following is the further improvement to above-mentioned technical proposal：
The spinning solution preparation process：It is 500~3000 by average degree of polymerization（Preferably the degree of polymerization is 1500~2500）'s
It is 10%~20% that polyvinyl alcohol dissolving, which prepares mass fraction,（Preferably mass fraction is 14%~18%）Polyvinyl alcohol（PVA）It is molten
Liquid；The PVA solution of preparation is added in the viscose glue stoste prepared by viscose process, spinning solution is obtained；The spinning solution
Middle PVA：The weight ratio of alpha cellulose is 10~90 in viscose glue stoste:90~10；Preferably 10-40:60-90.
The spinning moulding step：The spinning solution carries out spinning by coagulating bath after adjustment, the coagulating bath by
50~80g/L（It is preferred that 60~70g/L）Sulfuric acid, 1.0~10.0g/L（It is preferred that 2.0~7.0g/L）Zinc sulfate, 380~
415g/L（It is preferred that 400~410g/L）Sodium sulphate composition, solidification bath concentration drop be 5.0~10.0g/L, coagulation bath temperature
For 42~48 DEG C, spinneret draft -15%~10%（It is preferred that -15%~0%）, residence time of the strand in coagulating bath be 10~
15s；Spinning speed is 35-45m/s.
The drop of solidification bath concentration refers to the reduction of sulfuric acid concentration in shaping bath.
The damp and hot stretching step：The damp and hot drafting forming and drawing-off ratio include：Damp and hot stretching body lotion is by sulfuric acid
360~370g/L of sodium, 5~10g/L of sulfuric acid constitute, 90~95 DEG C of temperature, processing time of the tow in body lotion be 2.0~
3.0s, the damp and hot drafting multiple to fibre bundle is 30%~80%；
The tow process step：Washing process, 40~42 DEG C of water temperature；Desulfurization and alkali neutralisation treatment, 40~42 DEG C of temperature, hydrogen-oxygen
Change the concentration of sodium or sodium sulfite：4.0~6.0g/L；Oil bath concentration：4.0~7.0g/L；Bleaching levels：Hydrogen peroxide 0.5~
2.0 g/L.By the progress of the process, the processing to cellulosic component in composite fibre is realized, it is therefore prevented that subsequent handling pair
The destruction of cellulosic component, beneficial to the progress of subsequent handling；
The tow drying steps：Using hot blast as thermal source, 120~170 DEG C of temperature, tow contains into moisture during next step
Amount is 0.5~5.0%；
The present invention is that desulfurization bath, oil bath, drying and processing are carried out to fibre bundle, and prior art is usually that fiber after cut-out is carried out
Above-mentioned processing.
The xeothermic stretching step：Air bath, 200~210 DEG C of temperature, 70~90s of time, draw ratio 50%~80%；
The heat treatment shaping step：Quickly cooled down after air bath, 230~240 DEG C of temperature, 30~60s of time, heat treatment shaping
To 40-50 DEG C, macromolecular is fixed, keep thermal effectiveness；
The simple cross-linking step：The crosslinking bath is made up of or spoke at least one of 40~80g/L glyoxals or glutaraldehyde
Crosslinking is penetrated, crosslinking time is about 5~15min.Fibre bundle after simple crosslinking is through being cut to required length and by oiling, oil
Bath concentration：4.0~7.0g/L, obtains final products.
PVA/ cellulose composite fibers prepared by the present invention, specification is（1.33~3.33）dtex*（38~51）Mm, does strong
For 2.12~2.58cN/dtex, wet is 1.08~1.56cN/dtex by force, and wet modulus is 0.31-0.51 cN/dtex, hydroscopicity
For 7.6~12.0%, 10~20 DEG C of water resistance raising.
Present invention omits PVA solution precrosslink and further crosslinking bath, increase damp and hot stretching step, xeothermic stretching step
Suddenly, heat treatment shaping step and simple cross-linking step are combined, and tow process step is replaced to fiber treatment after cut-out
Step so that the PVA/ cellulose composite fibers of preparation, while the intensity of PVA/ cellulose composite fibers is ensured, improves multiple
The water resistance of condensating fiber.
The present invention uses above-mentioned technical proposal, compared with prior art, with following technique effect：
（1）The present invention omits PVA solution precrosslink and further crosslinking bath；PVA/ cellulose composite fibers are prepared, not only may be used
So that two kinds of components have complementary advantages, and both blending in structure, the PVA/ cellulose composite fibers of preparation can be realized
Dry strong >=2.12cN/dtex, wet strong >=1.08cN/dtex, wet modulus >=0.31cN/dtex.
（2）Composite fibre water resistance prepared by the present invention is high, and relative to existing patented technology, water resistance improves 10~20
DEG C, textile processibility is good, and hydroscopicity is 7.6~12.0%, and the present invention passes through the processes pair such as the xeothermic stretching of tow, heat treatment shaping
PVA carries out water resistance processing, then carries out PVA crosslinkings, further increases the water resistance of composite fibre.Meanwhile, preparation is answered
Condensating fiber, acid and alkali-resistance, weather resisteant are good, corrosion-resistant, be not afraid of and damage by worms, and the Exposure to Sunlight of long period is little to its intensity effect.
（3）A kind of preparation method of new PVA/ cellulose composite fibers is provided, the art of this patent be in viscose rayon and
Innovated on the basis of the moulding process of vinylon fibre, achieve preferable effect.For prior art, PVA solution is omitted
Precrosslink and further crosslinking bath, in the case where not making PVA/ cellulose composite fiber intensity, improve follow-up spinning effect
And working environment, improve spinning efficiency.
Brief description of the drawings
Fig. 1, PVA/ cellulose composite fibers preparation technology flow chart of the present invention.
Embodiment
The preferred embodiments of the present invention are illustrated below, it will be appreciated that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
Embodiment 1：A kind of preparation method of PVA/ cellulose composite fibers
Specification is as shown in Figure 1 for the specific preparation flow of 1.33dtex*38mm PVA/ cellulose composite fibers.
Comprise the following steps：
（1）Spinning solution preparation process：
The polyvinyl alcohol dissolving for being 500 by average degree of polymerization prepares the polyvinyl alcohol that mass fraction is 20%（PVA）Solution；Will system
Standby PVA solution is added in the viscose glue stoste prepared by viscose process, obtains spinning solution；PVA in spinning solution：Viscose glue is former
The weight ratio of alpha cellulose is 10 in liquid：90.
（2）Spinning moulding step
Spinning solution carries out spinning by coagulating bath after adjustment, and coagulating bath is by 80g/L sulfuric acid, 10.0g/L zinc sulfate,
380g/L sodium sulphate composition, the drop of solidification bath concentration is 10.0g/L, and coagulation bath temperature is 42 DEG C, spinneret draft 20%,
Residence time of the strand in coagulating bath is 10s, and spinning speed is 45m/s.
（3）Damp and hot stretching step
Damp and hot stretching body lotion is made up of sodium sulphate 360g/L, sulfuric acid 10.0g/L, 90 DEG C of temperature, processing of the tow in body lotion
Time is 2.0s, and damp and hot drafting multiple is 30%.
（4）Tow process step
Washing process, 40 DEG C of water temperature；Desulfurization and alkali neutralisation treatment, 40 DEG C of temperature, naoh concentration：6.0g/L；Oil bath concentration：
4.0g/L；Bleaching levels 2.0g/L；By the progress of the process, the processing to cellulosic component in composite fibre is realized, is prevented
Destruction of the subsequent handling to cellulosic component is stopped, beneficial to the progress of subsequent handling.
（5）Tow drying steps
Using hot blast as thermal source, 120 DEG C of temperature, moisture is 5.0% when tow enters next step.
（6）Xeothermic stretching step
Air bath, 200 DEG C of temperature, time 90s, draw ratio 80%.
（7）Heat treatment shaping step
40 DEG C are quickly cooled to after air bath, 230 DEG C of temperature, time 50s, heat treatment shaping, macromolecular is fixed, kept at heat
Manage effect.
（8）Simple cross-linking step
The crosslinking bath is made up of 40g/L glyoxals, and crosslinking time is about 15min.
The specification prepared by above-mentioned technique is the dry strong of 1.33dtex*38mm PVA/ cellulose composite fibers
2.12cN/dtex, wet strong 1.08cN/dtex, wet modulus 0.31cN/dtex, water resistance improve 10 DEG C, and textile processibility is good, inhale
Wet rate is 12.0%, acid and alkali-resistance, weather resisteant and good hygroscopicity, corrosion-resistant, be not afraid of and damage by worms.
Embodiment 2：A kind of preparation method of PVA/ cellulose composite fibers
Specification is as shown in Figure 1 for the specific preparation flow of 1.56dtex*38mm PVA/ cellulose composite fibers.
Comprise the following steps：
（1）Spinning solution preparation process
The polyvinyl alcohol dissolving for being 1000 by average degree of polymerization prepares the polyvinyl alcohol that mass fraction is 18%（PVA）Solution；Will system
Standby PVA solution is added in the viscose glue stoste prepared by viscose process, obtains spinning solution；PVA in spinning solution：Viscose glue is former
The weight ratio of alpha cellulose is 20 in liquid:80.
（2）Spinning moulding step
Spinning solution carries out spinning by coagulating bath after adjustment, and coagulating bath is by 75 g/L sulfuric acid, 7.6g/L zinc sulfate,
392g/L sodium sulphate composition, the drop of solidification bath concentration is 8.8g/L, and coagulation bath temperature is 44 DEG C, spinneret draft 12%, silk
Residence time of the bar in coagulating bath is 12s, and spinning speed is 42m/s.
（3）Damp and hot stretching step
The damp and hot drafting forming and drawing-off ratio include：Damp and hot stretching body lotion is by sodium sulphate 362g/L, sulfuric acid 9.1g/L groups
Into 91 DEG C of temperature, processing time of the tow in body lotion is 2.2s, and damp and hot drafting multiple is 39%.
（4）Tow process step
Washing process, 41 DEG C of water temperature；Desulfurization and alkali neutralisation treatment, 41 DEG C of temperature, concentration of sodium sulfite：5.2g/L；Oil bath concentration：
4.6g/L；Bleaching levels 1.8g/L；By the progress of the process, the processing to cellulosic component in composite fibre is realized, is prevented
Destruction of the subsequent handling to cellulosic component is stopped, beneficial to the progress of subsequent handling.
（5）Tow drying steps
Using hot blast as thermal source, 135 DEG C of temperature, moisture is 4.1% when tow enters next step.
（6）Xeothermic stretching step
Air bath, 205 DEG C of temperature, time 82s, draw ratio 72%.
（7）Heat treatment shaping step
42 DEG C are quickly cooled to after air bath, 233 DEG C of temperature, time 45s, heat treatment shaping, macromolecular is fixed, kept at heat
Manage effect.
（8）Simple cross-linking step
The crosslinking bath is made up of 48g/L glutaraldehydes, and crosslinking time is about 12min.
The specification prepared by above-mentioned technique is the dry strong by 2.25 of 1.56dtex*38mm PVA/ cellulose composite fibers
CN/dtex, wet strong 1.25cN/dtex, wet modulus 0.35cN/dtex, water resistance improve 13 DEG C, and textile processibility is good, hydroscopicity
In 11.2 %, acid and alkali-resistance, weather resisteant and good hygroscopicity are corrosion-resistant, be not afraid of and damage by worms.
Embodiment 3：A kind of preparation method of PVA/ cellulose composite fibers
Specification is as shown in Figure 1 for the specific preparation flow of 1.67dtex*38mm PVA/ cellulose composite fibers.
Comprise the following steps：
（1）Spinning solution preparation process
The polyvinyl alcohol dissolving for being 1700 by average degree of polymerization prepares the polyvinyl alcohol that mass fraction is 15%（PVA）Solution；Will system
Standby PVA solution is added in the viscose glue stoste prepared by viscose process, obtains spinning solution；PVA in spinning solution：Viscose glue is former
The weight ratio of alpha cellulose is 25 in liquid:75.
（2）Spinning moulding step
Spinning solution carries out spinning by coagulating bath after adjustment, and coagulating bath is by 68g/L sulfuric acid, 6.5g/L zinc sulfate,
398g/L sodium sulphate composition, the drop of solidification bath concentration is 7.6g/L, and coagulation bath temperature is 45 DEG C, spinneret draft 5.6
%, residence time of the strand in coagulating bath is 13s, and spinning speed is 40m/s.
（3）Damp and hot stretching step
The damp and hot drafting forming and drawing-off ratio include：Damp and hot stretching body lotion is by the g/L of sodium sulphate 365, sulfuric acid 8.3g/L groups
Into 92 DEG C of temperature, processing time of the tow in body lotion is 2.5s, and damp and hot drafting multiple is 45%.
（4）Tow process step
Washing process, 42 DEG C of water temperature；Desulfurization and alkali neutralisation treatment, 42 DEG C of temperature, concentration of sodium sulfite：4.8g/L；Oil bath concentration：
5.2g/L；Bleaching levels 1.5g/L；By the progress of the process, the processing to cellulosic component in composite fibre is realized, is prevented
Destruction of the subsequent handling to cellulosic component is stopped, beneficial to the progress of subsequent handling.
（5）Tow drying steps
Using hot blast as thermal source, 152 DEG C of temperature, moisture is 3.5% when tow enters next step.
（6）Xeothermic stretching step
Air bath, 206 DEG C of temperature, time 77s, draw ratio 65%.
（7）Heat treatment shaping step
44 DEG C are quickly cooled to after air bath, 235 DEG C of temperature, time 41s, heat treatment shaping, macromolecular is fixed, kept at heat
Manage effect.
（8）Simple cross-linking step
The crosslinking bath is made up of 55g/L glyoxal he 22g/L glutaraldehydes, and crosslinking time is about 10min.
The specification prepared by above-mentioned technique is the dry strong by 2.39 of 1.67dtex*38mm PVA/ cellulose composite fibers
CN/dtex, wet strong 1.41cN/dtex, wet modulus 0.41cN/dtex, water resistance improve 15 DEG C, and textile processibility is good, hydroscopicity
10.5%, acid and alkali-resistance, weather resisteant and good hygroscopicity are corrosion-resistant, be not afraid of and damage by worms.
Embodiment 4：A kind of preparation method of PVA/ cellulose composite fibers
Specification is as shown in Figure 1 for the specific preparation flow of 2.22 dtex*51mm PVA/ cellulose composite fibers.
Comprise the following steps：
（1）Spinning solution preparation process
The polyvinyl alcohol dissolving for being 2500 by average degree of polymerization prepares the polyvinyl alcohol that mass fraction is 12%（PVA）Solution；Will system
Standby PVA solution is added in the viscose glue stoste prepared by viscose process, obtains spinning solution；PVA in spinning solution：Viscose glue is former
The weight ratio of alpha cellulose is 32 in liquid:68.
（2）Spinning moulding step
Spinning solution carries out spinning by coagulating bath after adjustment, and coagulating bath is by 57 g/L sulfuric acid, 3.2g/L zinc sulfate,
406g/L sodium sulphate composition, the drop of solidification bath concentration is 6.2g/L, and coagulation bath temperature is 46 DEG C, the % of spinneret draft 0,
Residence time of the strand in coagulating bath is 14s, and spinning speed is 38m/s.
（3）Damp and hot stretching step
The damp and hot drafting forming and drawing-off ratio include：Damp and hot stretching body lotion is by the g/L of sodium sulphate 368, sulfuric acid 6.8g/L groups
Into 93 DEG C of temperature, processing time of the tow in body lotion is 2.7s, and damp and hot drafting multiple is 68%.
（4）Tow process step
Washing process, 41 DEG C of water temperature；Desulfurization and alkali neutralisation treatment, 41 DEG C of temperature, naoh concentration：4.4g/L；Oil bath concentration：
6.3g/L；Bleaching levels 0.9g/L；By the progress of the process, the processing to cellulosic component in composite fibre is realized, is prevented
Destruction of the subsequent handling to cellulosic component is stopped, beneficial to the progress of subsequent handling.
（5）Tow drying steps
Using hot blast as thermal source, 163 DEG C of temperature, moisture is 1.9% when tow enters next step.
（6）Xeothermic stretching step
Air bath, 208 DEG C of temperature, time 74s, draw ratio 56%.
（7）Heat treatment shaping step
47 DEG C are quickly cooled to after air bath, 237 DEG C of temperature, time 35s, heat treatment shaping, macromolecular is fixed, kept at heat
Manage effect.
（8）Simple cross-linking step
Crosslinking with radiation, crosslinking time is about 8min.
The specification prepared by above-mentioned technique is the dry strong by 2.43 of 2.22dtex*38mm PVA/ cellulose composite fibers
CN/dtex, wet strong 1.46cN/dtex, wet modulus 0.44cN/dtex, water resistance improve 18 DEG C, and textile processibility is good, hydroscopicity
8.8%, acid and alkali-resistance, weather resisteant and good hygroscopicity are corrosion-resistant, be not afraid of and damage by worms.
Embodiment 5：A kind of preparation method of PVA/ cellulose composite fibers
Specification is as shown in Figure 1 for the specific preparation flow of 3.33 dtex*51mm PVA/ cellulose composite fibers.
Comprise the following steps：
（1）Spinning solution preparation process：
The polyvinyl alcohol dissolving for being 3000 by average degree of polymerization prepares the polyvinyl alcohol that mass fraction is 10%（PVA）Solution；Will system
Standby PVA solution is added in the viscose glue stoste prepared by viscose process, obtains spinning solution；PVA in spinning solution：Viscose glue is former
The weight ratio of alpha cellulose is 40 in liquid:60.
（2）Spinning moulding step：
Spinning solution carries out spinning by coagulating bath after adjustment, and coagulating bath is by 50g/L sulfuric acid, 1.0g/L zinc sulfate,
415g/L sodium sulphate composition, the drop of solidification bath concentration is 5.0g/L, and coagulation bath temperature is 48 DEG C, spinneret draft -15%,
Residence time of the strand in coagulating bath is 15s, and spinning speed is 35m/s.
（3）Damp and hot stretching step
The damp and hot drafting forming and drawing-off ratio include：Damp and hot stretching body lotion is by sodium sulphate 370g/L, sulfuric acid 5.0g/L groups
Into 95 DEG C of temperature, processing time of the tow in body lotion is 3.0s, and damp and hot drafting multiple is 80%.
（4）Tow process step
Washing process, 40 DEG C of water temperature；Desulfurization and alkali neutralisation treatment, 42 DEG C of temperature, concentration of sodium sulfite：4.0g/L；Oil bath concentration：
7.0g/L；Bleaching levels 0.5g/L；By the progress of the process, the processing to cellulosic component in composite fibre is realized, is prevented
Destruction of the subsequent handling to cellulosic component is stopped, beneficial to the progress of subsequent handling.
（5）Tow drying steps
Using hot blast as thermal source, 170 DEG C of temperature, moisture is 0.5% when tow enters next step.
（6）Xeothermic stretching step
Air bath, 210 DEG C of temperature, time 70s, draw ratio 50%.
（7）Heat treatment shaping step
40 DEG C are quickly cooled to after air bath, 240 DEG C of temperature, time 30s, heat treatment shaping, macromolecular is fixed, kept at heat
Manage effect.
（8）Simple cross-linking step
The crosslinking bath is made up of 80g/L glutaraldehydes, and crosslinking time is about 5min.
The specification prepared by above-mentioned technique is the dry strong by 2.58 of 3.33dtex*51mm PVA/ cellulose composite fibers
CN/dtex, wet strong 1.56cN/dtex, wet modulus 0.51cN/dtex, water resistance improve 20 DEG C, and textile processibility is good, hydroscopicity
7.6%, acid and alkali-resistance, weather resisteant and good hygroscopicity are corrosion-resistant, be not afraid of and damage by worms.
The drop of heretofore described solidification bath concentration refers to the reduction of sulfuric acid concentration in shaping bath.
Unless specifically indicated, ratio of the present invention, is mass ratio, and the percentage is mass percent.
Finally it should be noted that：The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention,
Although the present invention is described in detail with reference to the foregoing embodiments, for those skilled in the art, it still may be used
To be modified to the technical scheme described in foregoing embodiments, within the spirit and principles of the invention, that is made appoints
What modification, equivalent substitution, improvement etc., should be included in the scope of the protection.
Claims (9)
1. a kind of preparation method of PVA/ cellulose composite fibers, it is characterised in that：The preparation method, including the spinning are former
Liquid preparation process, spinning moulding step, damp and hot stretching step, tow process step, tow drying steps, xeothermic stretching step,
Heat treatment shaping step, simple cross-linking step.
2. a kind of preparation method of PVA/ cellulose composite fibers according to claim 1, it is characterised in that：
The damp and hot stretching step, damp and hot stretching body lotion is made up of 360~370g/L of sodium sulphate, 5~10g/L of sulfuric acid, temperature
90~95 DEG C, processing time of the tow in body lotion is 2.0~3.0s, and damp and hot drafting multiple is 30%~80%.
3. a kind of preparation method of PVA/ cellulose composite fibers according to claim 1, it is characterised in that：
The xeothermic stretching step：Air bath, 200~210 DEG C of temperature, 70~90s of time, draw ratio 50%~80%.
4. a kind of preparation method of PVA/ cellulose composite fibers according to claim 1, it is characterised in that：
The heat treatment shaping step：Quickly cooled down after air bath, 230~240 DEG C of temperature, 30~60s of time, heat treatment shaping
To 40-50 DEG C.
5. a kind of preparation method of PVA/ cellulose composite fibers according to claim 1, it is characterised in that：
The tow process step：Washing process, 40~42 DEG C of water temperature；Then desulfurization and alkali neutralisation treatment, 40~42 DEG C of temperature,
The concentration of sodium hydroxide or sodium sulfite：4.0~6.0g/L；Then oil bath processing, oil bath concentration are carried out：4.0~7.0g/L；
Bleaching levels：The g/L of hydrogen peroxide 0.5~2.0.
6. a kind of preparation method of PVA/ cellulose composite fibers according to claim 1, it is characterised in that：The tow
Drying steps：Using hot blast as thermal source, 120~170 DEG C of temperature is dried to tow moisture 0.5~5.0%.
7. a kind of preparation method of PVA/ cellulose composite fibers according to claim 1, it is characterised in that：
The spinning solution preparation process：The polyvinyl alcohol dissolving for being 500~3000 by average degree of polymerization prepares mass fraction and is
10%~20% poly-vinyl alcohol solution；The poly-vinyl alcohol solution of preparation is added in the viscose glue stoste prepared by viscose process,
Prepare spinning solution；PVA in the spinning solution：The weight ratio of alpha cellulose is 10~90 in viscose glue stoste:90~10.
8. a kind of preparation method of PVA/ cellulose composite fibers according to claim 1, it is characterised in that：
The spinning moulding step：Coagulating bath is by 50~80g/L sulfuric acid, 1.0~10.0g/L zinc sulfate, 380~415g/L
Sodium sulphate composition, solidification bath concentration drop be 5.0~10.0g/L, coagulation bath temperature be 42~48 DEG C, spinneret draft-
15%~10%, residence time of the strand in coagulating bath is 10~15s.
9. a kind of preparation method of PVA/ cellulose composite fibers according to claim 1, it is characterised in that：
The simple cross-linking step：Crosslinking bath constitutes or radiated friendship by least one of 40~80g/L glyoxals or glutaraldehyde
Connection, crosslinking time is about 5~15min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710384820.9A CN107090607B (en) | 2017-05-26 | 2017-05-26 | Preparation method of PVA/cellulose composite fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710384820.9A CN107090607B (en) | 2017-05-26 | 2017-05-26 | Preparation method of PVA/cellulose composite fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107090607A true CN107090607A (en) | 2017-08-25 |
| CN107090607B CN107090607B (en) | 2020-12-01 |
Family
ID=59639810
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710384820.9A Active CN107090607B (en) | 2017-05-26 | 2017-05-26 | Preparation method of PVA/cellulose composite fiber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107090607B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107604454A (en) * | 2017-09-21 | 2018-01-19 | 成都新柯力化工科技有限公司 | A kind of environment-protecting clean preparation method of textile dedicated fiber cellulose fiber |
| CN107892768A (en) * | 2017-12-27 | 2018-04-10 | 成都新柯力化工科技有限公司 | A kind of high voltage direct current cable physical crosslinking type insulating materials and preparation method |
| CN108708224A (en) * | 2018-05-18 | 2018-10-26 | 山东恒联新材料股份有限公司 | A kind of production technology of paper substrate viscose glue composite material |
| CN109402774A (en) * | 2018-11-02 | 2019-03-01 | 恒天海龙（潍坊）新材料有限责任公司 | A kind of anti-fibrillated cellulose fibers and preparation method thereof |
| CN109664639A (en) * | 2018-11-28 | 2019-04-23 | 温州大学 | A kind of blended structure environmental protection macromolecule nib manufacturing process |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS525318A (en) * | 1975-06-30 | 1977-01-17 | Unitika Ltd | Process for producing super fine fibers |
| CN1772983A (en) * | 2004-11-10 | 2006-05-17 | 株式会社晓星 | Method for producing cellulose fiber |
| CN101240454A (en) * | 2008-03-14 | 2008-08-13 | 福建宏远集团有限公司 | Solvent preparation method of cellulose blend fiber and application thereof |
| CN103184582A (en) * | 2013-03-18 | 2013-07-03 | 山东海龙股份有限公司 | Preparation method of PVA composite high-strength high-modulus cellulose fiber |
-
2017
- 2017-05-26 CN CN201710384820.9A patent/CN107090607B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS525318A (en) * | 1975-06-30 | 1977-01-17 | Unitika Ltd | Process for producing super fine fibers |
| CN1772983A (en) * | 2004-11-10 | 2006-05-17 | 株式会社晓星 | Method for producing cellulose fiber |
| CN101240454A (en) * | 2008-03-14 | 2008-08-13 | 福建宏远集团有限公司 | Solvent preparation method of cellulose blend fiber and application thereof |
| CN103184582A (en) * | 2013-03-18 | 2013-07-03 | 山东海龙股份有限公司 | Preparation method of PVA composite high-strength high-modulus cellulose fiber |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107604454A (en) * | 2017-09-21 | 2018-01-19 | 成都新柯力化工科技有限公司 | A kind of environment-protecting clean preparation method of textile dedicated fiber cellulose fiber |
| CN107892768A (en) * | 2017-12-27 | 2018-04-10 | 成都新柯力化工科技有限公司 | A kind of high voltage direct current cable physical crosslinking type insulating materials and preparation method |
| CN107892768B (en) * | 2017-12-27 | 2020-10-16 | 上海凯波特种电缆料厂有限公司 | Physical crosslinking insulating material for high-voltage direct-current cable and preparation method thereof |
| CN108708224A (en) * | 2018-05-18 | 2018-10-26 | 山东恒联新材料股份有限公司 | A kind of production technology of paper substrate viscose glue composite material |
| CN108708224B (en) * | 2018-05-18 | 2021-01-05 | 山东恒联新材料股份有限公司 | Production process of paper-based viscose composite material |
| CN109402774A (en) * | 2018-11-02 | 2019-03-01 | 恒天海龙（潍坊）新材料有限责任公司 | A kind of anti-fibrillated cellulose fibers and preparation method thereof |
| CN109402774B (en) * | 2018-11-02 | 2021-10-15 | 恒天海龙（潍坊）新材料有限责任公司 | Anti-fibrillation cellulose fiber and preparation method thereof |
| CN109664639A (en) * | 2018-11-28 | 2019-04-23 | 温州大学 | A kind of blended structure environmental protection macromolecule nib manufacturing process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107090607B (en) | 2020-12-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107090607A (en) | A kind of preparation method of PVA/ cellulose composite fibers | |
| CN101492837B (en) | Process for producing bacteria cellulose fibre with high degree of polymerization | |
| CN101109115B (en) | Method of preparing protein modified polyacrylonitrile fibre | |
| CN101195933B (en) | Method for producing Lyocell fibre for tire cord | |
| JP7125814B2 (en) | Flame-retardant cellulosic fiber and method for preparing same | |
| CN100422404C (en) | Anti-wear polyvinyl alcohol aldehyde acetal fiber and its preparing method and use | |
| CN103266381A (en) | Preparation method for moisture-absorbing and heat-radiating polyacrylonitrile yarn | |
| CN101225552A (en) | Method for dissolving and processing wood/cotton bamboo hemp fibre by employing ionic liquid | |
| CN103184582B (en) | Preparation method of PVA composite high-strength high-modulus cellulose fiber | |
| CN102877158B (en) | Viscose filament yarn of feather keratin and bamboo fiber and method for producing same | |
| CN101580966B (en) | Chinlon 6 melt spinning method with ionic liquid as plasticiser | |
| CN110172754A (en) | A kind of preparation method of antigen fibrillated fibers element fiber | |
| CN109735949B (en) | Ultraviolet-resistant, moisture-absorbing and heating protein tencel fiber and preparation method thereof | |
| CN106012076B (en) | A kind of wet spinning preparation method of acetate fiber | |
| CN101240454A (en) | Solvent preparation method of cellulose blend fiber and application thereof | |
| CN103590140B (en) | A kind of imitative multiple polyisocyanate of linen look is combined short fibre and manufacture method thereof | |
| CN1081686C (en) | Wet PVA-crosslinking spinning technology | |
| CN102899741A (en) | Viscose filament yarns prepared from feather protein and wood fibers and preparation method thereof | |
| CN1287017C (en) | Chitin amine/polyviny vinyl alcohol composite fiber and its manufacturing method | |
| CN103122499B (en) | A kind of Splittable conjugate fiber and Superfine Fibre Fabric | |
| CN107075739B (en) | Lyocell crimped fiber | |
| CN1131346C (en) | Milk protein and polyvinyl alcohol copolymerized fibre and its preparing process | |
| JPH10331027A (en) | Regenerated cellulose fiber and production thereof | |
| CN103060939A (en) | Preparation method of cellulose acetate fiber through polybasic carboxylic acid crosslinking | |
| CN105113222A (en) | Superabsorbent fibers prepared from polyvinyl alcohol fibers and preparing method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211228 Address after: 261106 north of Xinsha Road, Guti street, Hanting District, Weifang City, Shandong Province Patentee after: Weifang Xinlong biomaterials Co.,Ltd. Address before: 261100 building 89, 1825 Hailong Road, Hanting District, Weifang City, Shandong Province Patentee before: HENGTIAN HAILONG (WEIFANG) NEW MATERIALS CO.,LTD. |
|
| TR01 | Transfer of patent right |