CN105001592A - Preparation method of polyacrylic acid grafted alkali lignin/phenolic aldehyde soft material - Google Patents
Preparation method of polyacrylic acid grafted alkali lignin/phenolic aldehyde soft material Download PDFInfo
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- CN105001592A CN105001592A CN201410592507.0A CN201410592507A CN105001592A CN 105001592 A CN105001592 A CN 105001592A CN 201410592507 A CN201410592507 A CN 201410592507A CN 105001592 A CN105001592 A CN 105001592A
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- polyacrylic acid
- alkali lignin
- acid grafted
- phenolic aldehyde
- soft material
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Abstract
The invention discloses a preparation method of a polyacrylic acid grafted alkali lignin/phenolic aldehyde soft material and relates to a manufacturing method of a water absorbent honeycomb material. According to the invention, mixed liquor of phenolic novolac resin and an auxiliary agent is immersed in a gel network of polyacrylic acid grafted alkali lignin, and soon afterwards foaming of phenolic resin is triggered so as to prepare the polyacrylic acid grafted alkali lignin/phenolic aldehyde soft material with interpenetrating of the gel network and a phenolic aldehyde open cell network. The invention has advantages as follows: the gel network of polyacrylic acid grafted alkali lignin endows the polyacrylic acid grafted alkali lignin/phenolic aldehyde soft material with fertilizer conservation and moisture retention properties; and the phenolic aldehyde resin open cell network endows the polyacrylic acid grafted alkali lignin/phenolic aldehyde soft material with functions of flood drainage and air permeability. Thus, the material can be used as a substitute for moisture retention flower mud or soil to be applied in the field of flower and special economic crops planting.
Description
Technical field
The present invention relates to a kind of manufacture method of cellular material of water suction, particularly relate to a kind of polyacrylic acid grafted alkali lignin/phenolic aldehyde soft material preparation method.
Background technology
Indoor and greenhouse flowers is planted in basin mostly.Due to flowerpot finite volume, the plant strain growth phase is long again, requires that compost has enough nutritive substances on the one hand, and also require that its space is suitable, have certain water retaining function and air permeability, therefore need manually to join soil, this soil is called as compost.Flowers are of a great variety, and habit is different, and compost should be allocated according to the character of flower growth habit and material.Clay containing mineral element and organic matter more, preserve moisture and fertility ability is strong and fertilizer efficiency is permanent.But spend the preparation precaution of soil a lot of, for bothersome effort a lot of working clan.In order to improve the performance of soil, Many researchers have developed conveniently, the substitute of lightweight, and now widely used is resol flower mud etc., but this flower mud fragility is large, and dry efflorescence after dehydration, is difficult to recycle.
A large amount of research work has been carried out, wherein polyacrylic polymer dominate (accounting for more than 50% of world-class High hydrophilous resin total amount) in the aspect such as kind, preparation method, performance, application of scholar to water-retaining agent of the country such as the U.S., Germany, France, Japan, China.But super absorbent resin has the shortcoming of expensive, difficult for biological degradation, bad mechanical property and salt tolerance difference, be difficult to be used widely in agricultural water suction and fertilizer slow release field.
The eighties in 20th century, investigator finds High hydrophilous resin and other materials compound can effectively improve the performances such as its salt tolerance, gel-strength, thermostability and water-absorbent.Biological material is blended/and cross-linking copolymer all can reduce material produce cost and give its biodegradability, but multipolymer also effectively can limit the deformation of the matrix material network system by crosslinking covalent bonds and hydrogen bond, therefore the mechanical property of multipolymer and controlled release properties are better than intermingling material.After this natural degradable polymer such as starch, Mierocrystalline cellulose, xylogen, inorganic clay and chitosan is used to prepare economical agricultural water-absorbing material.From the nineties in last century, Kok etc. introduce hydrophobic sulfate-reducing conditions after hydrogel microspheres realizes the slowly-releasing of aldicarb as filler, and the scholar of the country such as 20 th century America, France, India, Japan, China, Guinea conducts extensive research xylogen absorbent gel material.
Phenol formaldehyde foam is a kind of foam material obtained by foaming by resol.Compared with the material such as polystyrene material, pvc material, polyurethane material accounting for leading market status in early days, in fire-retardant, it has special premium properties.It is lightweight, and rigidity is large, good stability of the dimension, resistance to chemical attack, good heat resistance, difficult combustion, puts out certainly, low smog, flame resistant penetrates, and meets fire without unrestrained thing, cheap, be the ideal insulated heat lagging material of the industries such as electrical equipment, instrument, building, petrochemical complex, thus attract widespread attention.Phenolic materials has become one of kind with fastest developing speed in plastic material.Consumption constantly increases, and range of application constantly expands, and research and development is all quite active both at home and abroad.The maximum feature of phenolic materials is that fragility is large, and the toughness therefore improving it is the gordian technique of this material of application.Along with the appearance of energy dilemma, phenol receives resource, output and restriction in price.Researcher is extensively finding suitable phenol substitute and derivative thereof.
Alkali lignin is the by product deriving from the generation of paper-making pulping process, cheap, renewable, nontoxic, abundance; Due to xylogen activated after, there is the character of phenol, therefore nontoxic alkali lignin can be used for alternative poisonous, expensive phenol.In recent years, xylogen replaces the utilisation technology of phenol mainly to concentrate on the fields such as lignin modification sizing agent, the thermoplastic material of xylogen, film material and foam material.
Summary of the invention
The invention provides a kind of polyacrylic acid grafted alkali lignin/phenolic aldehyde soft material preparation method, the present invention immerses the gel network of polyacrylic acid grafted alkali lignin with the mixed solution of linear phenolic resin and auxiliary agent, cause Foaming of phenolic resin process subsequently, object is the polyacrylic acid grafted alkali lignin/phenolic aldehyde soft material of preparation gel network and phenolic aldehyde perforate network interpenetrating.The water retention property that this material is soft open-cell material, have simultaneously.According to These characteristics, the present invention introduces it spends mud application as water conservation in a particular embodiment.
Technical scheme of the present invention is that after flooding the cooling of polyacrylic acid grafted alkali lignin with the phenolic resin adhesive adding tensio-active agent, toughner and whipping agent, polyacrylic acid-g-alkali lignin/phenolic aldehyde (PAA-g-AL/PF) soft material is prepared in constant temperature drying foaming.The invention has the advantages that the gel network of polyacrylic acid grafted alkali lignin gives polyacrylic acid grafted alkali lignin/phenolic aldehyde soft material fertilizer conservation, performance of keeping humidity; And resol perforate network gives polyacrylic acid grafted alkali lignin/phenolic aldehyde soft material water drainage, ventilative function.Prepare soft material with the shortcoming that polyacrylic acid grafted alkali lignin net overcomes resol fragility large, therefore this material has the potential use being applied to the field of planting of flowers and special economic crop as water conservation flower mud or the substitute of soil.
Above-mentioned xylogen adopts one or two kinds and the above mixture of industrial lignin, Lignin from Alkaline Wheat Straw, straw lignin and sulfonated lignin.
Above-mentioned polyacrylic acid adopts polymerizable acrylic monomer or molecular weight to be 2000 ~ 5000Da polyacrylic acid.
The lower molecular weight soluble resin that above-mentioned phenolic resin adhesive adopts a kind of of phenol, cresols, xylenol, Resorcinol or two kinds and above mixture to prepare with formaldehyde or furfural polycondensation.
Above-mentioned tensio-active agent adopts one or two kinds and the above mixture of tween, sapn.
Above-mentioned toughner adopts one or two kinds and the above mixture of carboxy nitrile rubber, liquid acrylonitrile butadiene rubber, polyvinyl butyral acetal, polyethersulfone, polyphenylene oxide ketone, polyvinylpyrrolidone.
Above-mentioned whipping agent adopts one or two kinds and the above mixing of Skellysolve A, normal hexane, normal heptane, sherwood oil (petroleum naphtha), trichlorofluoromethane, Refrigerant 12, dichloro tetrafluoro ethane, sodium bicarbonate, bicarbonate of ammonia.
Accompanying drawing explanation
The polyacrylic acid grafted alkali lignin of Fig. 1/phenolic aldehyde soft material photo
Embodiment
Example 1
By the K-17 polyvinylpyrrolidone of the tween-80 of 1.5 mass parts, 4 mass parts, 1 mass parts 2, the polyacrylic acid grafted alkali lignin 6h of 10 mass parts is flooded after the Skellysolve A of 4-vulcabond, 3 mass parts and the pentamethylene of 3 mass parts mix with 50 mass parts resol, then hydrochloric acid is added, stir rapidly, put into the mould of about 62 DEG C, till being heated to material settling out, obtained polyacrylic acid grafted alkali lignin/phenolic aldehyde soft material A.The density of dry A material is 0.479g/cm
3, material water absorbent rate is 27 times, and under room temperature, moisture slowly-releasing number of days is 16 days.
Example 2
By the tween-80 of 0.5 mass parts, the K-17 polyvinylpyrrolidone of 5 mass parts, 1 mass parts 2, the Skellysolve A of 4-vulcabond, 8 mass parts mixes the rear polyacrylic acid grafted alkali lignin 6h flooding 3.5 mass parts with 50 mass parts resol, then hydrochloric acid is added, stir rapidly, put into the mould of about 60 DEG C, till being heated to material settling out, obtained polyacrylic acid grafted alkali lignin/phenolic aldehyde soft material B.The density of dry B material is 0.479g/cm
3, material water absorbent rate is 27 times, and under room temperature, moisture slowly-releasing number of days is 16 days.
Example 3
By the K-17 polyvinylpyrrolidone of the tween-80 of 1.5 mass parts, 4 mass parts, 1 mass parts 2, the Skellysolve A of 4-vulcabond, 3 mass parts mixes the rear polyacrylic acid grafted alkali lignin 6h flooding 10 mass parts with 50 mass parts resol, then add hydrochloric acid to stir rapidly, put into the mould of about 62 DEG C, till being heated to material settling out, obtained polyacrylic acid grafted alkali lignin/phenolic aldehyde soft material C.The density of dry C material is 0.396g/cm
3, material water absorbent rate is 39.9 times, and under room temperature, moisture slowly-releasing number of days is 21 days.
Example 4
The polyacrylic acid grafted alkali lignin 6h of 7 mass parts is flooded after the glycerol of the K-17 polyvinylpyrrolidone of the tween-80 of 3 mass parts, 8 mass parts, 10 mass parts, the Skellysolve A of 8 mass parts being mixed with 100 mass parts phenolic aldehyde, then add hydrochloric acid to stir rapidly, put into the mould of about 60 DEG C, till being heated to material settling out, obtained polyacrylic acid grafted alkali lignin/phenolic aldehyde soft material D.The density of dry D material is 0.409g/cm
3, material water absorbent rate is 16.3 times, and under room temperature, moisture slowly-releasing number of days is 10 days.
Example 5
The polyacrylic acid grafted alkali lignin 6h of 10 mass parts is flooded after the glycerol of the K-17 polyvinylpyrrolidone of the tween-80 of 3 mass parts, 4 mass parts, 5 mass parts, the Skellysolve A of 8 mass parts being mixed with 50 mass parts phenolic aldehyde, then add successively and then add hydrochloric acid and stir rapidly, put into the mould of about 60 DEG C, till being heated to material settling out, obtained polyacrylic acid grafted alkali lignin/phenolic aldehyde soft material E.The density of dry E material is 0.6013g/cm
3, material water absorbent rate is 19.29 times, and under room temperature, moisture slowly-releasing number of days is 15 days.
Example 6
The polyacrylic acid grafted alkali lignin 6h of 6 mass parts is flooded after the K-17 polyvinylpyrrolidone of the tween-80 of 3 mass parts, 4 mass parts, the Skellysolve A of 8 mass parts being mixed with 100 mass parts resol, then add hydrochloric acid to stir rapidly, put into the mould of about 60 DEG C, till being heated to material settling out, obtained polyacrylic acid grafted alkali lignin/phenolic aldehyde soft material F.The density of dry F material is 0.3865g/cm
3, material water absorbent rate is 14.18 times, and under room temperature, moisture slowly-releasing number of days is 8 days.
Example 7
The polyacrylic acid grafted alkali lignin 6h of 5 mass parts is flooded after being mixed with 100 mass parts resol by the Skellysolve A of the K-17 polyvinylpyrrolidone of the tween-80 of 3 mass parts, 4 mass parts, 10 mass parts glycerol, 8 mass parts, then add hydrochloric acid to stir rapidly, put into the mould of about 60 DEG C, till being heated to material settling out, obtained polyacrylic acid grafted alkali lignin/phenolic aldehyde soft material G.The density of dry G material is 0.1044g/cm
3, material water absorbent rate is 16.85 times, and under room temperature, moisture slowly-releasing number of days is 14 days.
Claims (8)
1. polyacrylic acid grafted alkali lignin/phenolic aldehyde soft material preparation method, it is characterized in that: this soft material is that to flood polyacrylic acid grafted alkali lignin with the phenolic resin blend adding tensio-active agent, toughner and whipping agent cold, polyacrylic acid-g-alkali lignin/phenolic aldehyde (PAA-g-AL/PF) soft material is prepared in constant temperature foaming.
2. above-mentioned xylogen according to claim 1 adopts one or two kinds and the above mixture of industrial lignin, Lignin from Alkaline Wheat Straw, straw lignin and sulfonated lignin.
3. above-mentioned polyacrylic acid according to claim 1 adopts polymerizable acrylic monomer or molecular weight to be 2000 ~ 5000Da polyacrylic acid.
4. above-mentioned resol according to claim 1 adopts the lower molecular weight soluble resin that a kind of of phenol, cresols, xylenol, Resorcinol or two kinds and above mixture prepare with formaldehyde or furfural polycondensation.
5. above-mentioned tensio-active agent according to claim 1 adopts one or two kinds and the above mixture of tween, sapn.
6. above-mentioned toughner according to claim 1 adopts one or two kinds and the above mixture of carboxy nitrile rubber, liquid acrylonitrile butadiene rubber, polyvinyl butyral acetal, polyethersulfone, polyphenylene oxide ketone, polyvinylpyrrolidone.
7. above-mentioned whipping agent according to claim 1 adopts one or two kinds and the above mixing of Skellysolve A, normal hexane, normal heptane, sherwood oil (petroleum naphtha), trichlorofluoromethane, Refrigerant 12, dichloro tetrafluoro ethane, sodium bicarbonate, bicarbonate of ammonia.
8. polyacrylic acid grafted alkali lignin/phenolic aldehyde soft material according to claim 1 has fertilizer conservation, water conservation draining, the function such as ventilative.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108704588A (en) * | 2018-06-29 | 2018-10-26 | 广西壮族自治区林业科学研究院 | A kind of preparation method of microencapsulation acidic aqueous solution |
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| CN1431275A (en) * | 2003-01-21 | 2003-07-23 | 武汉理工大学 | Multi-functional macromolecule composite material for sand-fixation vegetation and its preparing method |
| CN103483613A (en) * | 2013-09-26 | 2014-01-01 | 临沂市泰尔化工科技有限公司 | Preparation method for degradable urea formaldehyde foam plant culture substrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1431275A (en) * | 2003-01-21 | 2003-07-23 | 武汉理工大学 | Multi-functional macromolecule composite material for sand-fixation vegetation and its preparing method |
| CN103483613A (en) * | 2013-09-26 | 2014-01-01 | 临沂市泰尔化工科技有限公司 | Preparation method for degradable urea formaldehyde foam plant culture substrate |
Non-Patent Citations (1)
| Title |
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| 马艳丽等: "聚丙烯酸接枝碱木质素基铁肥的制备及其缓释性能", 《农业工程学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108704588A (en) * | 2018-06-29 | 2018-10-26 | 广西壮族自治区林业科学研究院 | A kind of preparation method of microencapsulation acidic aqueous solution |
| CN108704588B (en) * | 2018-06-29 | 2020-10-09 | 广西壮族自治区林业科学研究院 | Preparation method of microencapsulated acidic aqueous solution |
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