CN1072969A - The viscose grafting, copolymerization and modification prepares the wool-like fiber method - Google Patents
The viscose grafting, copolymerization and modification prepares the wool-like fiber method Download PDFInfo
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- CN1072969A CN1072969A CN 92112125 CN92112125A CN1072969A CN 1072969 A CN1072969 A CN 1072969A CN 92112125 CN92112125 CN 92112125 CN 92112125 A CN92112125 A CN 92112125A CN 1072969 A CN1072969 A CN 1072969A
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- monomer
- viscose
- potassium permanganate
- graft copolymerization
- copolymerization
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Abstract
The present invention relates to a kind of viscose and vinyl monomer, the process of graft copolymerization.
With potassium permanganate is that initator makes viscose and a kind of monomer or two monomer-grafted copolymerization first step carry out pre-oxidation with potassium permanganate earlier, and the potassium permanganate consumption is 0.063～1.58% of a cellulose consumption.Second step added monomer in the presence of air, carry out polymerization in the acidic aqueous solution that emulsifying agent or emulsifier-free are arranged.50～90 ℃ of reaction temperatures, 20～100 minutes time.The advantage of process of the present invention is that the monomer consumption is few, and liquor ratio is little, and graft copolymerization is carried out in the presence of air smoothly, and homopolymers is lower than 1%, and technology is simple, is suitable for suitability for industrialized production.
Description
The present invention relates to the process that a kind of viscose and graft copolymerization of vinyl monomer modification prepare wool-like fiber.
Graft copolymerization is one of important channel of cellulose fibre modification, and the graft copolymerization product had both kept the original characteristic of cellulose fibre, makes it have some new capability of synthetic polymer side chain again.
The Graft Copolymerization of Cellulose reaction free radical polymerisation process that adopt at first produce free radical, trigger monomer graft copolymerization then more on the cellulose macromolecule chain.Often produce a large amount of homopolymers in the process of the whole bag of tricks initiation grafting copolymerization, this is that the Graft Copolymerization of Cellulose modification is difficult to realize one of industrialized key issue.Potassium permanganate is a kind of reagent cheap and easy to get, also has unique advantage with potassium permanganate as initator: the thorough eccysis of potassium permanganate available water before graft reaction that fiber surface is excessive, there is not potassium permanganate in the solution, thereby avoided direct trigger monomer to produce homopolymerization, owing to suppressed the generation of homopolymers effectively, thereby made commercial Application become possibility.About with potassium permanganate being the special public 36-17634 of photograph of patent Japan that initator causes vinyl monomer and cellulose graft, and disclosed cellulose and graft copolymerization of vinyl monomer among Chinese patent (the publication number 1055185A) 90101692.6, its process must be given and be fed nitrogen earlier, get rid of oxygen, and consume a large amount of monomers, or adding a large amount of organic solvents, the reaction time reaches 5～8 hours.The purpose of this invention is to provide a kind of graft copolymerization technology of simplification, the monomer consumption is few, and the reaction time is short, without organic solvent, and can react under the system that does not need first deoxygenation.
Graft copolymerization proposed by the invention is realized as follows:
A kind of monomer or two monomer are that initator and viscose graft copolymerization are to carry out in a reactor that has an internal circulation apparatus with potassium permanganate, the potassium permanganate consumption is 0.063～1.58% of a fibre weight, in still, prepare earlier the liquor potassic permanganate of desired concn before the reaction, again fiber is put into solution, period minute, be heated to 30～70 ℃, be incubated 5～20 minutes, give oxidation.Remove unnecessary liquor potassic permanganate, wash fiber with water 1～3 time, to cleaning solution colourless till.Add a kind of monomer or two monomer of fibre weight 50～70% then, and add a certain amount of acid solution, the acid concentration that makes reactant liquor is 0.001～0.10mol/L, adding the water yield is 8～20 times (weight) of fibre weight, adds emulsifying agent or does not add emulsifying agent, circulates 5～20 minutes, be heated to 50～90 ℃, reacted 20～100 minutes, and reacted China, emit raffinate, the abundant washing the fibre of water, centrifuge dripping, drying makes the modified fibre product.Fiber weightening finish 25～55%, homopolymers is lower than 1%.
Adopt the fluffy softness of graft copolymer fibre product of process preparation provided by the invention, rich hair is loyal, ABRASION RESISTANCE, and elastic return, DIMENSIONAL STABILITY and hygroscopicity are compared with raw fiber and all are significantly improved.
Embodiment one
With 4.8kg(over dry 4.0kg) viscose puts into the liquor potassic permanganate that concentration is 0.004mol/L, and solution amount is 13 times of viscose weight, circulates 3～5 minutes, is heated to 60 ℃, is incubated 10 minutes, removes excess liquid, washes fiber with water 3 times.Add about 63kg of entry and 2.4kg acrylonitrile period minute, add sulfuric acid then, making the reactant liquor acid concentration is 0.024mol/L, circulates 5 minutes, be warming up to 57 ℃, be incubated 32 minutes, emit raffinate, the abundant washing the fibre of water, centrifuge dries, drying, graft fibres weightening finish 54.1%.
Embodiment two
With 4.5kg(over dry 4.0kg) viscose puts into the liquor potassic permanganate that concentration is 0.0032mol/L, and solution amount is 13 times of viscose weight, removes excess liquid, washes with water 3 times.Add about 63kg of entry and acrylonitrile 2.1kg, add sulfuric acid then, making the reactant liquor acid concentration is 0.0125mol/L.Circulated 5 minutes, and be warming up to 53 ℃, be incubated 64 minutes.Water fully washs, and centrifuge dries, drying, graft fibres weightening finish 28.2%.
Embodiment three
With 5.3kg(over dry 4.7kg) viscose puts into the liquor potassic permanganate that concentration is 0.004mol/L, and solution amount is 13 times of viscose weight, circulates 5 minutes, is warming up to 59 ℃, is incubated 20 minutes, removes excess liquid, washes fiber with water 3 times.Add about 63kg of entry and the about 20g of OP-10 emulsifying agent, add styrene 2.7kg, add acetic acid, making the reactant liquor acid concentration is 0.05mol/L, and is warming up to 90 ℃, is incubated 86 minutes.The abundant washing the fibre of water, centrifuge dries, drying, graft fibres weightening finish 51.2%.
Embodiment four
With 5.3kg(over dry 4.7kg) viscose puts into the liquor potassic permanganate that concentration is 0.0032mol/L, and solution amount is 13 times of viscose weight, circulates 3 minutes, is heated to 68 ℃, is incubated 20 minutes, removes excess liquid, washes fiber with water 3 times.Add about 63kg of entry and OP～about 30g of 10 emulsifying agents, add styrene 1.7kg then, acrylonitrile 1.2kg adds nitric acid behind the mixing, and making entire reaction liquid acid concentration is 0.025mol/L, is warming up to 82 ℃, is incubated 30 minutes.Reaction finishes, the abundant washing the fibre of water, and centrifuge dries, drying, graft fibres weightening finish 49.5%.
Embodiment five
As embodiment one, use nitric acid instead and make catalyst, also can reach effect same.
Embodiment six
As embodiment four, do not add emulsifying agent, also can reach effect same.
Claims (3)
1, a kind of viscose modified technique, it is included in the acid medium, makes initator with potassium permanganate, makes viscose and graft copolymerization of vinyl monomer, and its technology characteristics is as follows:
(1) give oxidation technology:
Gave the oxidation viscose 5～20 minutes with potassium permanganate solution, oxidizing temperature is 30～70 ℃, and the potassium permanganate consumption is 0.063～1.58% of a cellulose consumption, gives the excessive potassium permanganate of flush away fiber surface after the oxidation.
(2) viscose after oxidation in the presence of air, carries out graft copolymerization with a kind of monomer or two monomer in the acidic aqueous solution that emulsifying agent or emulsifier-free are arranged.
2, according to the technology described in the claim 1, the acid concentration that it is characterized in that the aqueous solution of the used a kind of monomer of graft copolymerization or two monomers is 0.001～0.10mol/L, and the reaction temperature of graft copolymerization is 50～90 ℃, 20～100 minutes reaction time.
3,, it is characterized in that preparing a kind of monomer or the needed water yield of two monomer solution and be 8～20 times of cellulose according to the technology described in the claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92112125 CN1030619C (en) | 1992-10-05 | 1992-10-05 | Prepn. method for imitation wool fibre by grafting, copolymerization and modification of viscose fibre |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92112125 CN1030619C (en) | 1992-10-05 | 1992-10-05 | Prepn. method for imitation wool fibre by grafting, copolymerization and modification of viscose fibre |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1072969A true CN1072969A (en) | 1993-06-09 |
| CN1030619C CN1030619C (en) | 1996-01-03 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92112125 Expired - Fee Related CN1030619C (en) | 1992-10-05 | 1992-10-05 | Prepn. method for imitation wool fibre by grafting, copolymerization and modification of viscose fibre |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1030619C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1068887C (en) * | 1997-02-25 | 2001-07-25 | 中国科学院大连化学物理研究所 | Synthesis of affinity film medium using cellulose as substrate |
| CN100434448C (en) * | 2005-11-04 | 2008-11-19 | 中国科学院化学研究所 | Modified electrode face finish material based on sodium carboxymethyl cellulose, and preparation method |
| CN106946240A (en) * | 2016-01-06 | 2017-07-14 | 江苏博凯环境科技有限公司 | The technique that a kind of environmentally conscious materialses are modified |
-
1992
- 1992-10-05 CN CN 92112125 patent/CN1030619C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1068887C (en) * | 1997-02-25 | 2001-07-25 | 中国科学院大连化学物理研究所 | Synthesis of affinity film medium using cellulose as substrate |
| CN100434448C (en) * | 2005-11-04 | 2008-11-19 | 中国科学院化学研究所 | Modified electrode face finish material based on sodium carboxymethyl cellulose, and preparation method |
| CN106946240A (en) * | 2016-01-06 | 2017-07-14 | 江苏博凯环境科技有限公司 | The technique that a kind of environmentally conscious materialses are modified |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1030619C (en) | 1996-01-03 |
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