CN1584154A

CN1584154A - Natural high-polymer polymer modified fibre and filament preparing method

Info

Publication number: CN1584154A
Application number: CN 200410022685
Authority: CN
Inventors: 丰纪述
Original assignee: Individual
Current assignee: Individual
Priority date: 2004-06-03
Filing date: 2004-06-03
Publication date: 2005-02-23
Anticipated expiration: 2024-06-03
Also published as: CN1243141C

Abstract

The maufacture method of a kind of wavegenes macromolecule polymer modified fibre and long-thread. After made filature original liquid, crank the original liquid out thread. The character is the original liquid can be done like this: (1) Let crylic acid and propylene acyl-amine react, we can receive poly(crylic acid-propylene acyl-amine) copolymer P(AA/AAM); and the let the polymer and PVA occur aggregation react, we can receive poly-vinyl-alcohol-poly(crylic acid/propylene acyl-amine) table polymer PVA-P(AA/AAM); (2) let the poly-vinyl-alcohol-poly(crylic acid/propylene acyl-amine) table polymer PVA-P(AA/AAM) and savageness macromolecule polymer mix or aggregate, we can receive filature original liquid. the filature received form this invention has the characteristic of good harmonization ability, large quantity of the thread model, high anti-hotwater and high respring ability.

Description

Production method of natural high molecular polymer modified fiber and filament

Technical Field

The invention relates to a method for producing natural high molecular polymer modified fiber and filament.

Background

The problem of dressing is solved by people in the world nowadays, and the development of synthetic fiber is obtained. The raw materials of the synthetic fiber are mainly from petroleum and natural gas, the resources are not renewable, and the production process inevitably causes pollution to the environment. Today's dressing requirements are gradually changed, and from the previous requirements of body shielding and warm keeping, comfort, moisture absorption, air permeability, sanitation, health care and less pollution are further required, and the synthetic fibers developed to the present cannot meet the increasing requirements of people. Therefore, the fiber is made of natural high molecular polymer, and the fiber made of the natural high molecular polymer has the performances of moisture absorption, air permeability, good dyeing property, affinity with human bodies, health care and the like, not only makes up for the defects of the natural fiber, but also improves the defects of the performance of the synthetic fiber, thereby having the characteristics of the fiber. The natural high molecular polymer can be plant protein, such as soybean protein, peanut protein, rapeseed protein, cottonseed protein, corn protein and polypeptide of the plant protein, or animal protein, such as cocoon layer and pupa of spinning insect, feather and skin residue of animal, or chitosan (chitin). In order to improve the quality of the fibers produced, there are two methods available: firstly, acrylonitrile and the natural high molecular polymer are adopted for graft copolymerization to obtain modified plant protein or modified animal protein; and secondly, blending modified or unmodified plant protein or animal protein with polyvinyl alcohol (PVA) to obtain spinning stock solution, and spinning the spinning stock solution into silk. However, in practical applications, it has been found that when polyvinyl alcohol (PVA) is blended with the above-mentioned modified or unmodified plant protein or animal protein, the spinning dope has poor stability and compatibility, and the filament has poor hot water resistance and poor rebound resilience, thus having disadvantages.

Disclosure of Invention

The invention aims to improve the modification method of the natural high molecular polymer and provide a novel production method of natural high molecular polymer modified fiber and filament.

The basic technical scheme of the invention is as follows: reacting acrylic acid with acrylamide to obtain poly (acrylic acid-acrylamide) copolymer P (AA/AAM); copolymerizing the poly (acrylic acid-acrylamide) copolymer P (AA/AAM) and polyvinyl alcohol PVA to obtain polyvinyl alcohol-poly (acrylic acid/acrylamide) block copolymer PVA-P (AA/AAM); blending or copolymerizing the obtained polyvinyl alcohol-poly (acrylic acid/acrylamide) block copolymer PVA-P (AA/AAM) with the existing natural high molecular polymer to obtain spinning solution, wherein the weight ratio of the used natural high molecular polymer to the polyvinyl alcohol-poly (acrylic acid/acrylamide) block copolymer PVA-P (AA/AAM) is 3-5: 7-5, and in the proportion, the net contents of the natural high molecular polymer and the polyvinyl alcohol-poly (acrylic acid/acrylamide) block copolymer PVA-P (AA/AAM) are calculated according to 100%; finally, the spinning dope is spun into filaments according to the existing spinning method.

In the present invention, the natural polymer blended or copolymerized with the polyvinyl alcohol-poly (acrylic acid/acrylamide) block copolymer PVA-P (AA/AAM) may be directly plant protein (such as plant protein in konjac powder), modified plant protein or polypeptide of plant protein after graft copolymerization with acrylonitrile, modified animal protein (such as modified silk protein or modified pupa protein) after graft copolymerization with acrylonitrile, chitosan extracted from animal protein, etc. The plant protein can be soybean protein, peanut protein, rapeseed protein, cottonseed protein, corn protein and other plant proteins, and the animal protein can be cocoon shell, pupa of silking insect, feather and skin residue of animal, etc.

The plant protein can be grafted and copolymerized with acrylonitrile according to the existing method to obtain modified plant protein, and can also be acetylated, phosphorylated and hydrolyzed into polypeptide according to the existing method. When the modified vegetable protein and PVA-P (AA/AAM) are blended, the ratio of the modified vegetable protein to the PVA-P is 3-5: 7-5 (weight ratio), and a spinning solution with the concentration of 14-20% can be prepared. When the polypeptide of the vegetable protein is copolymerized with PVA-P (AA/AAM), the ratio of the polypeptide to the PVA-P is 3-5: 7-5 (weight ratio), and a spinning solution with the concentration of 14-20% can be prepared. In the above mixture ratio, the net content of PVA-P (AA/AAM) is 100%, and the net contents of modified vegetable protein and polypeptide of vegetable protein are 100%.

The animal silk protein can be prepared by the prior method: such as mulberry cocoon, castor cocoon, camphor cocoon, tussah cocoon, giant silkworm cocoon, etc. can be rinsed with sodium carbonate, acetylated, dissolved in saturated solution of sodium thiocyanate or zinc chloride, copolymerized with acrylonitrile, and oxidized and reduced with redox initiator to obtain modified silk protein. The ratio of the modified silk protein to the PVA-P (AA/AAM) is 3-5: 7-5 (weight ratio). In the above formulation, the net content of PVA-P (AA/AAM) is 100%, and the net content of modified silk protein is 100%.

The animal pupa protein can be prepared by the existing method: for example, the pupae of various spinning insects, such as silkworm, castor silkworm, camphor silkworm, tussah silkworm and wild silkworm, are crushed, extracted by using a dilute NaOH solution, filtered, the filtrate is subjected to oil-water separation, oil phase extraction is performed, oil and fat are extracted by using an oil phase, pupa protein is extracted by using a water phase, and filter residue is used for extracting chitosan. The obtained pupa protein can also be acetylated and then grafted and copolymerized by acrylonitrile to obtain the modified pupa protein. The modified pupa protein and PVA-P (AA/AAM) are blended, the ratio of the modified pupa protein to the PVA-P (AA/AAM) is 3-5: 7-5 (weight ratio), and the spinning solution with the concentration of 18-20% can be prepared. In the mixture ratio, the net content of PVA-P (AA/AAM) is calculated according to 100 percent, and the net content of the modified pupa protein is calculated according to 100 percent.

In the process of the present invention, acrylic acid is copolymerized with acrylamide to give poly (acrylic acid/acrylamide) P (AA/AAM) according to the following reaction equation:

the block copolymerization of polyvinyl alcohol-poly (acrylic acid/acrylamide) to obtain PVA-P (AA/AAM) has the following reaction equation:

in the copolymerization of acrylic acid and acrylamide and the block copolymerization of polyvinyl alcohol-poly (acrylic acid/acrylamide), water and redox initiator can be added in proper amount. Ammonium persulfate and sodium bisulfite can be added as an initiator when acrylic acid and acrylamide are copolymerized, and ammonium ceric nitrate and the like can be added as an initiator when polyvinyl alcohol-poly (acrylic acid/acrylamide) is copolymerized in a block mode.

In the present invention, P (AA/AAM) and PVA-P (AA/AAM) can be produced in the following manner: 70-80 parts (by weight, the net content is 100%) of acrylic acid, 20-30 parts (by weight, the net content is 100%), 250-350 parts of water and 0.5-1.0 part (by weight, the net content is 100%) of redox initiator (ammonium persulfate or sodium bisulfite) are reacted to obtain poly (acrylic acid/acrylamide) copolymer P (AA/AAM) with the concentration of about 25%. 3 parts of poly (acrylic acid/acrylamide) copolymer P (AA/AAM) with the concentration of about 25 percent are copolymerized with 15 parts of polyvinyl alcohol PVA, 82 parts of water and 0.5 part of initiator (cerium ammonium nitrate can be used) to obtain the polyvinyl alcohol-poly (acrylic acid/acrylamide) block copolymer PVA-P (AA/AAM) with the concentration of 16 to 17 percent.

It should be noted that the ratio of acrylic acid to acrylamide for preparing P (AA/AAM) can be selected within the range of 10-50: 90-50 (weight ratio, net content is 100%) according to the performance of the fiber. The reaction to prepare P (AA/AAM) is carried out in an aqueous solution, and when 300 parts by weight of water are added to 100 parts by weight of the monomers (acrylic acid + acrylamide), 0.5 part of potassium persulfate and 0.25 part of potassium metabisulfite may be used as initiators, under the conditions of pH 4-6, temperature about 60 ℃ and reaction time about 1 hour. Meanwhile, when the block copolymer PVA-P (AA/AAM) is prepared, the proportion of the polyvinyl alcohol to the poly (acrylic acid/acrylamide) copolymer can be selected according to the requirements of fiber performance, such as 7-6: 3-4.

When the polyvinyl alcohol-poly (acrylic acid/acrylamide) block copolymer is blended or copolymerized with the natural polymer, a spinning dope can be obtained.

When the natural high molecular polymer adopts the polypeptide of the plant protein, the polypeptide of the plant protein can be extracted from the plant protein according to the prior art. The reaction equation of the graft copolymerization of the polypeptide of the vegetable protein and the polyvinyl alcohol-poly (acrylic acid/acrylamide) is as follows:

as the initiator in the above reaction, ammonium ceric nitrate, ceric sulfate, ammonium persulfate, sodium sulfite and the like can be used.

When the natural high molecular polymer adopts plant protein or animal protein which is graft copolymerized with acrylonitrile, the graft copolymerization of the acrylonitrile and the protein (the plant protein or the animal protein) can be directly realized by utilizing the prior art. The mechanism of the grafting reaction of proteins with acrylonitrile is currently unknown. Proteins are structurally complex and acrylonitrile may react at multiple groups of the protein. It has been described that acrylonitrile and protein ZnCL have been mentioned earlier₂In solution grafting, CHINON in Japan is also a silk-like silk product grafted by acrylonitrile and casein, but the reaction mechanism is still unknown.

In the invention, the process of spinning the spinning solution into filaments can directly adopt the existing technical process, for example, a large spray head with ten thousand holes in a tile shape is adopted to spin long filament bundles into short fibers (fiber), or the fibers are cut and drawn into wool tops (stable), or a small spinneret with dozens of holes one-hundred holes can be used to spin long filaments (filament), but the spinning process is not the improvement point of the invention, so the process is not repeated.

Compared with the prior similar method, the method of the invention adopts the polyvinyl alcohol-poly (acrylic acid/acrylamide) block copolymer to be blended or copolymerized with the modified or unmodified natural high molecular polymer, so that the obtained spinning solution has better stability and compatibility, the spun silk has large modulus, the hot water resistance is improved, and the rebound resilience is better. The method of the invention is the cross application of various disciplines of biochemistry, polymer chemistry and synthetic fiber technology.

The present invention will be further described with reference to the following examples, but the present invention is not limited to the examples.

Detailed Description

Example 1: the natural high molecular polymer adopted in this embodiment is animal pupa protein, namely modified pupa protein, which is obtained by graft copolymerization of acrylonitrile.

The polyvinyl alcohol-poly (acrylic acid/acrylamide) block copolymer PVA-P (AA/AAM) is prepared according to the technical scheme introduced by the invention: taking 70Kg of acrylic acid, 30Kg of acrylamide and 280Kg of water, stirring, adding 0.5Kg of ammonium persulfate under the inert gas at about 60 ℃, then adding 0.25Kg of sodium bisulfite, and keeping the pH value to be more than 7. Stirring for 1-2 hours to obtain a copolymer p (AA/AAM), and measuring the solid content. Then 20Kg of PVA (average degree of polymerization 1750, fiber grade) is taken and added with water to swell to prepare 15 percent solution, and the temperature is raised to 98 ℃ under the sealing condition. Taking 75Kg of PVA 15% solution and 30Kg of P (AA/AAM) 15% solution, stirring, adding redox initiator (0.5 Kg of ammonium persulfate is added, and then 0.25Kg of sodium bisulfite is added), reacting at 95 ℃ for 1.2 hours to obtain PVA-P (AA/AAM).

Meanwhile, the modified pupa protein is prepared in advance, and the process is briefly described as follows: taking 100Kg of dry mulberry silkworm pupa, crushing, soaking in warm water at 70-80 ℃, keeping the bath ratio at 10, adjusting the pH value to 10 by NaOH, stirring for 1 hour, filtering, standing the filtrate, putting the filtrate into an oil-water separator, extracting oil from an oil phase, adjusting the pH value of anisoelectric point of the filtrate to 4.5 by an aqueous phase liquid, and precipitating the pupa protein. Washing the filter residue with water with pH of 10, treating the filtrate as above, and extracting chitin from the filter residue. Rinsing the precipitated pupa protein, dehydrating, measuring the solid content, allowing the oil content to be 3-5%, controlling the pH of the water-soluble bath solution to be 6.5-7, preparing a 17% solution, adding Acrylonitrile (AN) with the amount of 20-30% of the pupa protein under stirring, reacting for 1-2 hours by using AN oxidation-reduction initiator, and keeping the temperature to be less than 70 ℃. Obtaining the pupa protein grafted by acrylonitrile, namely the modified pupa protein.

Preparing 7Kg (by solid) of PVA-P (AA/AAM) and 3Kg (by 100% of both net contents) of modified pupa protein into 18% of spinning solution, stirring for 2 hours at the temperature of 95 ℃ and under the negative pressure of about 0.9bar, filtering, preserving heat and standing under the negative pressure of about 0.9bar, and defoaming.

Then, the existing technical process is directly adopted, and the obtained spinning solution is used for wet spinning: spinning speed 6M/Min, negative stretching 0.9, stretching 2.6 times after bath, wet-heat stretching 1.8 times, dry stretching 1.4 times, and total stretching 6.55 times. Coagulation bath Na₂SO₄d is 1.3, t is 48 ℃, the soaking is 1.5M, the pH is 4, the wet heat treatment bath d is 1.27, t is 90-95 ℃, and the dry heat stretching temperature is 200 ℃. The RP of the silk is 85-90 ℃, and the RP is more than 105 ℃ after post-treatment.

The prepared pupa protein silk is light brown yellow, such as the luster of earth silk, flexibility and drapability, the strength is 4-5 gf/d, the elongation is 16-20%, the hygroscopicity is 9-11%, the dyeing property is excellent, the pupa protein silk can be dyed by acid dye andreactive dye, the pupa protein silk can resist sunlight, and the pupa protein silk is more resistant to chemicals than silk.

Example 2: the natural high molecular polymer adopted in this embodiment is animal silk protein, i.e., modified silk protein, which is graft-copolymerized with acrylonitrile.

In this example, a polyvinyl alcohol-poly (acrylic acid/acrylamide) block copolymer PVA-P (AA/AAM) was prepared in the same manner as in example 1.

Meanwhile, the castor silk is rinsed by sodium carbonate and acetylated by the prior art, and is dissolved in saturated solution of sodium thiocyanate or zinc chloride to be copolymerized with acrylonitrile, and the modified silk protein is obtained by a redox initiator.

40Kg of modified silk protein of ricinus communis and 60Kg of PVA-P (AA/AAM) (by solid content) are prepared into 18 percent of spinning solution, the spinning solution is stirred for 1 to 2 hours under negative pressure, kept warm and kept stand, defoamed and spun according to a wet method, and the process is similar to that of the embodiment 1.

Example 3: the natural high molecular polymer adopted in this embodiment is a polypeptide of a plant protein.

In this example, a polyvinyl alcohol, a poly (acrylic acid/acrylamide) block copolymer PVA-P (AA/AAM), was prepared in a similar manner to example 1: 80Kg of acrylic acid, 20Kg of acrylamide and 320Kg of water are taken and stirred, 0.5Kg of ammonium persulfate is added under the inert gas at about 60 ℃, and then 0.25Kg of sodium bisulfite is added to keep the pH value more than 7. Stirring for 1-2 hours to obtain a copolymer p (AA/AAM), and measuring the solid content. Then 20Kg of PVA (average degree of polymerization 1750, fiber grade) is taken and added with water to swell to prepare 15 percent solution, and the temperature is raised to 98 ℃ under the sealing condition. Taking 75Kg of PVA 15% solution and 30Kg of P (AA/AAM) 15% solution, stirring, adding 0.5Kg of redox initiator ammonium persulfate and 0.25Kg of sodium bisulfite, reacting at 95 ℃ for 1.8 hours to obtain PVA-P (AA/AAM).

Preparing 20% spinning solution from 40Kg of rapeseed protein polypeptide and 60Kg (by solid) of PVA-P (AA/MM) (both net contents are 100%), adding initiator (such as ammonium ceric nitrate) to react for 1 hr, and spinning by the above wet method. The spun silk is light brown to dark brown, does not need dyeing, does not fade after long-time washing, and has adjustable color.

The rapeseed protein polypeptide used in this embodiment can also be replaced by a cottonseed protein polypeptide.

Example 4: the natural high molecular polymer adopted in this embodiment is a plant protein obtained by graft copolymerization with acrylonitrile, i.e., a modified plant protein.

Then, 40Kg of modified soybean protein and 60Kg of PVA-P (AA/AAM) (net content is calculated by 100%) are prepared into 18% of spinning stock solution, the spinning stock solution is stirred under negative pressure for 1-2 hours, the spinning stock solution is kept warm and is defoamed, and the spun silk is ivory yellow, is flexible and dangling, is elegant like silk, has luster like silk, has strength higher than that of real silk, and has sunlight resistance, hygroscopicity and dyeing property.

The modified soy protein used in this example may also be replaced with modified peanut protein.

Example 5: the natural polymer used in this embodiment is chitosan.

Then, 30Kg chitosan and 70Kg PVA-P (AA/AAM) (both net contents are calculated by 100%) are dissolved in 0.5M acetic acid solution to prepare 16% concentration; PVA-P (AA/AAM)Dissolved in water to make 16% concentration. Mixing the two, stirring under negative pressure, filtering, standing for defoaming, and wet spinning, wherein the first bath is Na₂SO₄+ NaOH, pH 10, d 1.3, t 48 ℃, Na for the second bath₂SO₄D is 1.25, t is about 80 ℃, and pH is 7.

The advantages of this yarn are: high strength, high resilience and antibacterial effect.

Claims

1. A production method of natural high molecular polymer modified fiber and filament, after preparing spinning dope, spinning the spinning dope into filament, characterized in that the spinning dope is prepared by the following method:

(1) reacting acrylic acid with acrylamide to obtain poly (acrylic acid-acrylamide) copolymer P (AA/AAM); then the poly (acrylic acid-acrylamide) copolymer P (AA/AAM) and polyvinyl alcohol PVA are subjected to copolymerization reaction to obtain polyvinyl alcohol-poly (acrylic acid/acrylamide) block copolymer PVA-P (AA/AAM);

(2) blending or copolymerizing the obtained polyvinyl alcohol-poly (acrylic acid/acrylamide) block copolymer PVA-P (AA/AAM) and a natural high molecular polymer to obtain a spinning solution, wherein the weight ratio of the natural high molecular polymer to the polyvinyl alcohol-poly (acrylic acid/acrylamide) block copolymer PVA-P (AA/AAM) is 3-5: 7-5, and the net content of the natural high molecular polymer and the polyvinyl alcohol-poly (acrylic acid/acrylamide) block copolymer PVA-P (AA/AAM) is 100%.

2. The method according to claim 1, wherein the natural high molecular polymer is a modified natural high molecular polymer obtained by graft copolymerization of acrylonitrile.

3. The method as set forth in claim 1, wherein said natural high molecular polymer is animal pupa protein graft-copolymerized with acrylonitrile, i.e. modified pupa protein.

4. The method as set forth in claim 1, wherein said natural high molecular polymer is modified silk protein which is animal silk protein graft-copolymerized with acrylonitrile.

5. The method according to claim 1, wherein the natural high molecular weight polymer is a polypeptide of a plant protein.

6. The method as set forth in claim 1, wherein said natural high molecular polymer is a modified vegetable protein which is a vegetable protein obtained by graft-copolymerizing acrylonitrile.

7. The method of claim 1, wherein the natural polymer is chitosan.