CN108822268A - Milk protein modified acrylic fibre slurries synthesis technology - Google Patents
Milk protein modified acrylic fibre slurries synthesis technology Download PDFInfo
- Publication number
- CN108822268A CN108822268A CN201810558135.8A CN201810558135A CN108822268A CN 108822268 A CN108822268 A CN 108822268A CN 201810558135 A CN201810558135 A CN 201810558135A CN 108822268 A CN108822268 A CN 108822268A
- Authority
- CN
- China
- Prior art keywords
- casein
- modified acrylic
- milk protein
- acrylic fibre
- protein modified
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
-
- 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
- D01F4/00—Monocomponent artificial filaments or the like of proteins; Manufacture thereof
- D01F4/04—Monocomponent artificial filaments or the like of proteins; Manufacture thereof from casein
-
- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/40—Modacrylic fibres, i.e. containing 35 to 85% acrylonitrile
-
- 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
- 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
- D01F8/08—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyacrylonitrile as constituent
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Artificial Filaments (AREA)
Abstract
The present invention relates to milk protein modified acrylic fibre slurries synthesis technology, casein pretreatments：Casein is placed in urea liquid and carries out swelling pretreatment；Polymerization process：The casein filtering of swelling is placed in solution, acrylonitrile is added and initiator carries out polymerization reaction, obtains milk protein modified acrylic fibre.Compared with prior art, the present invention unfolds protein macromolecule sufficiently the pretreatment of casein, is easier to be polymerize with acrylonitrile monemer, and stable reaction, without side reaction.
Description
Technical field
The present invention relates to fiber production fields, synthesize more particularly, to a kind of milk protein modified acrylic fibre slurries
Technique.
Background technique
Milk protein modified acrylic fibre is a kind of side that milk casein (casein) is passed through graft copolymerization
Method grafts the new modified fiber of formation on polyacrylonitrile molecular side chain.In the patent 00116211.X delivered, by bone
Frame compound milk casein and acrylonitrile or acrylonitrile and vinyl unsaturated monomer are dissolved in liquor zinci chloridi, with oxidation
Reduction initiating system carries out graft copolymerization.Although the patent substitutes inorganic initiator using organic initiators, solves zinc chloride
The recycling problem of solvent and reduce environmental pollution.But since redox initiation system is made of two kinds of chemical substances,
It has the disadvantages that in the actual production process：1) more complicated for operation than single initiator；2) it adds speed and reaction rate is difficult to
Control；3) consumption is big, higher cost.
Summary of the invention
It is modified that it is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of milk proteins
Polyacrylonitrile fibre slurries synthesis technology.
The purpose of the present invention can be achieved through the following technical solutions：
Milk protein modified acrylic fibre slurries synthesis technology, using following steps：
(1) casein pre-processes：Casein is placed in urea liquid and carries out swelling pretreatment；
(2) polymerization process：The casein filtering of swelling is placed in solution, acrylonitrile is added and initiator is polymerize
Reaction, obtains milk protein modified acrylic fibre.
The concentration of urea liquid described in step (1) is 5-50wt%, and the mass ratio of casein and urea liquid is 1:20
~1:5, the temperature of swelling pretreatment is 25-95 DEG C, time 0.5-12h.
Solution described in step (2) is concentration 40wt% to saturation sodium thiocyanate solution, casein and sodium thiocyanate solution
Mass ratio be 3~15:100, the initiator is azodiisobutyronitrile, and the mass ratio of casein and acrylonitrile is 1~4:6~
9, the additional amount of initiator is 0.1~2wt% of solution total amount.
In former redox initiation system, using azodiisobutyronitrile as alternative initiator.Azodiisobutyronitrile is azo
Type radical initiator, azo-initiator stable reaction are first order reactions, and without side reaction, and medium temperature decomposes and is suitble to casein
Reaction, relatively good control, stabilization easy to operate such as use azo initiator, do not use other such as zinc chloride polar solvent, if made
It is acid too strong with the better solvent of polarity, it is easy to cause new decomposition of initiator, protein (casein) can also decomposed, this
Application is solved the above problems by using Sodium Thiocyanate Solvent to cooperate azodiisobutyronitrile.
It is more obvious using azo initiator advantage and fairly simple to the pretreatment of casein.Casein is isoelectric point
For the bisexual protein of pH4.8, exist in milk with the composite form of Dicalcium Phosphate, tricalcium phosphate or both, constructs pole
For complexity, up to now without completely specified molecular formula, molecular weight is higher, about 57000-375000.If the work by
Skill does not pre-process casein, then dissolubility of the casein in Sodium Thiocyanate Solvent is poor, will lead to polymerization reaction not
Thoroughly, the problems such as degree of polymerization and protein content of casein and acrylonitrile polymer are not easy to control, seriously affects aralac
Quality.It is pre- using urea by being pre-processed to casein for the use for cooperating the above azo initiator and dicyandiamide solution
Casein is handled, its swelling is made, and the macromolecular chain in protein is allowed to obtain softness and unfold.Then it enters back into solvent and neutralizes third
Alkene nitrile monomer is polymerize, to solve the problems, such as casein indissoluble in Sodium Thiocyanate Solvent.
Compared with prior art, the present invention has the following advantages that：
1, using a kind of initiator, cost is reduced；
2, azo-initiator stable reaction, without side reaction；
3, technique preferably controls, easy to operate；
4, unfold protein macromolecule sufficiently the pretreatment of casein, be easier to be polymerize with acrylonitrile monemer.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Embodiment 1
3 grams of casein are put into 25 DEG C of 15 gram 5% of urea liquid and are impregnated 0.5 hour.By the casein mistake of swelling
Leaching goes out and is dissolved in the solution being made of 40 grams of sodium sulfocyanates and 60 grams of water, and 12 grams of acrylonitrile, 0.1 gram of idol are added while stirring
Nitrogen bis-isobutyronitrile, 65 DEG C of reaction temperature, the reaction time 1 hour, polymer molecular weight 5.9 ten thousand, viscosity 108 was moored, solid content
6.4%.
Embodiment 2
6 grams of casein are put into 60 DEG C of 75 gram 25% of urea liquid and are impregnated 6 hours.The casein of swelling is filtered
It takes out and is dissolved in the solution being made of 100 grams of sodium sulfocyanates and 100 grams of water, 18 grams of acrylonitrile, 2 grams of azos are added while stirring
Bis-isobutyronitrile, 70 DEG C of reaction temperature, the reaction time 2 hours, polymer molecular weight 6.3 ten thousand, viscosity 182 was moored, solid content 7.5%.
Embodiment 3
8 grams of casein are put into 95 DEG C of 160 gram 50% of urea liquid and are impregnated 12 hours.By the casein mistake of swelling
Leaching goes out and is dissolved in the solution being made of 180 grams of sodium sulfocyanates and 120 grams of water, and 16 grams of acrylonitrile, 6 grams of idols are added while stirring
Nitrogen bis-isobutyronitrile, 75 DEG C of reaction temperature, the reaction time 3 hours, polymer molecular weight 6.7 ten thousand, viscosity 227 was moored, solid content
8.9%.
Embodiment 4
Milk protein modified acrylic fibre slurries synthesis technology, using following steps：
(1) casein pre-processes：It is to control casein in 50wt% urea liquid and urea is molten that casein, which is placed in concentration,
The mass ratio of liquid is 1:5, temperature is 95 DEG C, swelling pretreatment 0.5h；
(2) polymerization process：The filtering of the casein of swelling is placed in the sodium thiocyanate solution of saturation, be added acrylonitrile and
The mass ratio of initiator azodiisobutyronitrile progress polymerization reaction, casein and sodium thiocyanate solution is 15:100, casein and third
The mass ratio of alkene nitrile is 4:9, the additional amount of azodiisobutyronitrile is the 2wt% of solution total amount, is prepared by polymerization reaction
Milk protein modified acrylic fibre.
Embodiment 5
Milk protein modified acrylic fibre slurries synthesis technology, using following steps：
(1) casein pre-processes：It is to control casein in 5wt% urea liquid and urea is molten that casein, which is placed in concentration,
The mass ratio of liquid is 1:20, temperature is 25 DEG C, swelling pretreatment 12h；
(2) polymerization process：The casein filtering of swelling is placed in the sodium thiocyanate solution of concentration 40wt%, is added third
The mass ratio of alkene nitrile and initiator azodiisobutyronitrile progress polymerization reaction, casein and sodium thiocyanate solution is 3:100, casein
Mass ratio with acrylonitrile is 1:6, the additional amount of azodiisobutyronitrile is the 0.1wt% of solution total amount, by polymerization reaction system
It is standby to obtain milk protein modified acrylic fibre.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (10)
1. milk protein modified acrylic fibre slurries synthesis technology, which is characterized in that the technique uses following steps：
(1) casein pre-processes：Casein is placed in urea liquid and carries out swelling pretreatment；
(2) polymerization process：The casein filtering of swelling is placed in solution, acrylonitrile is added and initiator polymerize instead
It answers, obtains milk protein modified acrylic fibre.
2. milk protein modified acrylic fibre slurries synthesis technology according to claim 1, which is characterized in that step
(1) concentration of urea liquid described in is 5-50wt%.
3. milk protein modified acrylic fibre slurries synthesis technology according to claim 1, which is characterized in that step
(1) mass ratio of casein described in and urea liquid is 1:20~1:5.
4. milk protein modified acrylic fibre slurries synthesis technology according to claim 1, which is characterized in that step
(1) temperature of swelling pretreatment is 25-95 DEG C in, time 0.5-12h.
5. milk protein modified acrylic fibre slurries synthesis technology according to claim 1, which is characterized in that step
(2) solution described in is sodium thiocyanate solution.
6. milk protein modified acrylic fibre slurries synthesis technology according to claim 5, which is characterized in that described
The concentration of sodium thiocyanate solution is 40wt% to saturation.
7. milk protein modified acrylic fibre slurries synthesis technology according to claim 5, which is characterized in that described
The mass ratio of casein and sodium thiocyanate solution is 3~15:100.
8. milk protein modified acrylic fibre slurries synthesis technology according to claim 1, which is characterized in that step
(2) initiator described in is azodiisobutyronitrile.
9. milk protein modified acrylic fibre slurries synthesis technology according to claim 1, which is characterized in that step
(2) mass ratio of casein described in and acrylonitrile is 1~4:6~9.
10. milk protein modified acrylic fibre slurries synthesis technology according to claim 1, which is characterized in that step
Suddenly the additional amount of initiator described in (2) is 0.1~2wt% of solution total amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810558135.8A CN108822268A (en) | 2018-06-01 | 2018-06-01 | Milk protein modified acrylic fibre slurries synthesis technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810558135.8A CN108822268A (en) | 2018-06-01 | 2018-06-01 | Milk protein modified acrylic fibre slurries synthesis technology |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108822268A true CN108822268A (en) | 2018-11-16 |
Family
ID=64146815
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810558135.8A Pending CN108822268A (en) | 2018-06-01 | 2018-06-01 | Milk protein modified acrylic fibre slurries synthesis technology |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108822268A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109576816A (en) * | 2018-12-24 | 2019-04-05 | 郑宇� | A kind for the treatment of process recycling milk protein fiber |
| CN112680812A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Polyacrylonitrile-based milk protein fiber and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5270384A (en) * | 1989-05-08 | 1993-12-14 | American Cyanamid Company | Surface-modified polyacrylonitrile fibrous substrates |
| CN1088085A (en) * | 1992-12-15 | 1994-06-22 | 北京矿冶研究总院 | Preparation method of bactericidal, oil-proof and dirt-removing skin-care emulsion and product |
| CN1412356A (en) * | 2001-10-16 | 2003-04-23 | 上海丝绸（集团）有限公司 | Preparation method of silkworm chrysalis protein-acrylonitrile graft copolymer fibre spinning raw liquor |
| CN1478929A (en) * | 2003-07-01 | 2004-03-03 | 郝小生 | Animal and vegetable protein and acrylonitrile grafting copolymerization fiber and its manufacturing method |
| CN101747479A (en) * | 2008-12-15 | 2010-06-23 | 上海正家牛奶丝科技有限公司 | Synthesis process of graft copolymerized fiber slurry of collagen and acrylonitrile |
-
2018
- 2018-06-01 CN CN201810558135.8A patent/CN108822268A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5270384A (en) * | 1989-05-08 | 1993-12-14 | American Cyanamid Company | Surface-modified polyacrylonitrile fibrous substrates |
| CN1088085A (en) * | 1992-12-15 | 1994-06-22 | 北京矿冶研究总院 | Preparation method of bactericidal, oil-proof and dirt-removing skin-care emulsion and product |
| CN1412356A (en) * | 2001-10-16 | 2003-04-23 | 上海丝绸（集团）有限公司 | Preparation method of silkworm chrysalis protein-acrylonitrile graft copolymer fibre spinning raw liquor |
| CN1478929A (en) * | 2003-07-01 | 2004-03-03 | 郝小生 | Animal and vegetable protein and acrylonitrile grafting copolymerization fiber and its manufacturing method |
| CN101747479A (en) * | 2008-12-15 | 2010-06-23 | 上海正家牛奶丝科技有限公司 | Synthesis process of graft copolymerized fiber slurry of collagen and acrylonitrile |
Non-Patent Citations (5)
| Title |
|---|
| 朱洪法: "《精细化工常用原材料手册》", 31 December 2003, 金盾出版社 * |
| 李华雨: "丙烯睛-酪素在硫氰酸钠浓溶液中接枝共聚的研究", 《河南化工》 * |
| 李广宇等: "《胶粘剂原材料手册》", 31 August 2004, 国防工业出版社 * |
| 王箴: "《化工词典》", 31 December 1979, 化学工业出版社 * |
| 马世昌: "《化学物质辞典》", 30 April 1999, 陕西科学技术出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109576816A (en) * | 2018-12-24 | 2019-04-05 | 郑宇� | A kind for the treatment of process recycling milk protein fiber |
| CN112680812A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Polyacrylonitrile-based milk protein fiber and preparation method thereof |
| CN112680812B (en) * | 2019-10-18 | 2024-01-23 | 中国石油化工股份有限公司 | Polyacrylonitrile-based milk protein fiber and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108822268A (en) | Milk protein modified acrylic fibre slurries synthesis technology | |
| CN110563876B (en) | Hydrophobic association anionic polyacrylamide water-in-oil emulsion and preparation method thereof | |
| CN102649828B (en) | Preparation method of ultrahigh-hydrolysis-degree polyacrylamide | |
| CN104693360A (en) | Method for preparing high-strength hydrogel | |
| EP3882284B1 (en) | Acrylamide copolymer and preparation method therefor and use thereof | |
| CN104448135B (en) | Preparing method for heat resistance and salt tolerance polyacrylamide used in oil field | |
| Bayazeed et al. | Synthesis and Application of New Thickerners Part I: Preparation of Poly (Acrylic Acid)‐Starch Graft Copolymer | |
| US4282340A (en) | Polymerization process for preparation of acrylamide homopolymers with redox catalyst | |
| CN106395915B (en) | A kind of synthetic method of poly-ferric sulfate chloride | |
| CN102675509B (en) | Preparation method of nonionic polyacrylamide (NPAM) | |
| CN117209655A (en) | Preparation method of salt-resistant polyacrylamide | |
| CN105174536B (en) | The method and its preprocess method of a kind of utilization brown oxide waste liquid production plating-grade copper oxide | |
| CN106146748A (en) | A kind of water-soluble fluorine-containing dissaving polymer thinner and preparation method thereof | |
| CN104710583A (en) | Preparation method for high-strength hydrogel | |
| CN102219879B (en) | Method for producing polyacrylamide emulsion | |
| CN104693338A (en) | Acrylic hyperdispersing agent and preparation method thereof | |
| CA1235840A (en) | Preparing aqueous hydrolyzed polymer solutions for oil recovery applications | |
| ATE309274T1 (en) | METHOD FOR PRODUCING AQUEOUS POLYMER DISPERSIONS | |
| US4433122A (en) | Stopping/restarting free radical polymerizations | |
| CN102382229B (en) | Preparation method of chlorinated polyether resin with core-shell structure | |
| CN112252057A (en) | Preparation method of composite anionic polyacrylamide printing and dyeing thickener | |
| DE2455036C3 (en) | Process for the production of pulverulent, water-soluble, linear polymers or copolymers with a very high molecular weight | |
| CN101519471A (en) | Emulsion polymerization preparation method of chlorinated polyether resin | |
| DE2849370A1 (en) | METHOD FOR PRODUCING 2,2'-AZOBIS- (2,4-DIMETHYL-4-METHOXYPENTANNITRILE) | |
| CN107556432A (en) | A kind of method added molecular weight regulator and prepare paper grade (stock) cationic retention aid filter aid |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181116 |
|
| RJ01 | Rejection of invention patent application after publication |