CN1064213C - Water absorbing bond linkage polymer plant growth regulators and the preparation thereof - Google Patents
Water absorbing bond linkage polymer plant growth regulators and the preparation thereof Download PDFInfo
- Publication number
- CN1064213C CN1064213C CN97101624A CN97101624A CN1064213C CN 1064213 C CN1064213 C CN 1064213C CN 97101624 A CN97101624 A CN 97101624A CN 97101624 A CN97101624 A CN 97101624A CN 1064213 C CN1064213 C CN 1064213C
- Authority
- CN
- China
- Prior art keywords
- plant growth
- present
- water absorbing
- growth regulators
- chloride
- 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.)
- Expired - Fee Related
Links
Images
Abstract
The present invention relates to a bond-linkage type water absorption macromolecule plant growth regulator. The structural formula is the right formula disclosed in the specification, and the molecular weight is 2000 to 5000. The present invention comprises the following preparation technology: the water bath, circumfluence and reaction of the polyacrylic acid and thionyl chloride are realized by magnetic stir; polypropylene acyl chloride is obtained by reduced pressure distillation; the circumfluence and reaction of the polypropylene acyl chloride and methylene chloride solution of N-benzoyl-N'-para hydroxybenzene thiourea are realized by stir; pyridinium and a phase transfer catalyst are added; then, filtration is realized, and wash is realized by the methylene chloride; the final products are obtained by dryness in a drying oven. The slow-release performance and long effect of the present invention are enhanced, the present invention simultaneously has water absorption, water retention and plant growth regulation effect and is especially suitable for the growth of crops in dry regions, and the present invention has the advantages of stable preparation technology and short, simple and reliable preparation process.
Description
The present invention relates to a kind of binding type water absorbing and retaining properties polymer plant growth conditioning agent and preparation technology thereof.
China's population accounts for about 23% of the world total, and arable area only accounts for 7% of the world total, has 1/3rd province per capita cultivated land very to lack 1 mu of less than.Along with the continuous increase of population, the minimizing day by day in arable land, grain in short supply more and more obvious.Solve food problem and realize high yield, mainly can adopt technology such as genetic engineering technology, rhizosphere technology and appliable plant growth regulator.Plant growth regulator is meant the organic compound beyond the nutriment, and they may produce in plant corpus, or from external application, infiltrates that there is regulating action the back to growth and development of plants in the plant corpus.The consumption of plant growth regulator is little, but its effect is big, can stratification, control bloom, delay with control aging course, increase output, improvement crop quality, increase resistance etc.In this field, the most valued is the conditioning agent that can make crop yield, and they have shown very big efficient in agricultural production.Therefore plant growth regulator is current domestic and international chemical boundary, biological educational circles and agronomy circle priority fields of study, is considered to one of measure of 21 century agricultural super high-yielding, will effectively promote " green revolution " for the second time.The research of plant growth regulator has had nearly 50 years history.At present, the whole world has 40 big chemical industrial companies of family studying plant growth regulator approximately, wherein great majority are in the U.S., and its pesticide research planning being become three big fields from original seven big field adjustment as DOW chemical company is Insecticides (tech) ﹠ Herbicides (tech) and plant growth regulator.Domestic, Jiangsu Province is more advanced, and a little research work have also been done by Shenyang Chemical Engineering Inst, Nankai University etc.All there is the small lot batch manufacture of minority kind in provinces such as Guangdong, Guangxi, Hubei in recent years, but far can not meet the demands.And domestic research at present mainly rests in the research of water-absorbing resin or simple plant growth regulator; as a disclosed plant growth regulators N in the little molecule plant growth regulator N-benzoyl-N '-p-hydroxybenzene thiocarbamide of homemade cross linked sodium polyacrylate, Northwest Normal University development and the Chinese patent 93102043, the high-efficiency water-absorbing rooting fertilizer of N dimethylamine base ethyl-4-chloro-α-isopropyl benzyl carboxylate hydrochloride and Linxing Sci. ﹠ Tech. Dev. Co., Jilin Prov.'s development etc.Above-mentioned Sodium Polyacrylate does not promote the plant growing effect and do not possess except that having suction, water retention.Though the little molecule plant growth regulator of Northwest Normal University's development can be regulated plant growing, it is loss, fugitive easily.N, N dimethylamine base ethyl-4-chloro-α-isopropyl benzyl carboxylate hydrochloride is though have significant effect to the volume increase of plant, its long-acting slow-release poor performance, nothing suction, water retention.The high-efficiency water-absorbing rooting fertilizer of Linxing Sci. ﹠ Tech. Dev. Co., Jilin Prov. development is that the compound preparation that fertility, promotion are grown to one is taken root, increased in collection suction, water conservation, the stimulation of developing on former water absorbing agent (folk prescription) basis, this product is an embedding type compound preparation, and its slow release is poor.
Thereby the objective of the invention is in order to provide a kind of little molecule plant growth regulator is chemically bound in by active ester bond to make its slow release and long-lasting enhancing on the water-absorbing resins, and have suction, water retention, plant growth regulation simultaneously in the water absorbing bond linkage polymer plant growth regulators of one.
Another object of the present invention also is to provide the preparation technology of a kind of process stabilizing, short, the simple key polymer plant growth conditioning agent of flow process.
Purpose of the present invention can realize by following measure: a kind of structural formula of water absorbing bond linkage polymer plant growth regulators is:
Its molecular weight is 2000-5000.It is poly-that its preparation technology contains the following step:
-in container, press 1: weight ratio (5-15) adds polyacrylic resin and thionyl chloride, and the water-bath back flow reaction is 7-10 hour under the magnetic agitation; Decompression distillation is removed excessive thionyl chloride and is got poly acryloyl chloride then, and its molecular weight is 2000-5000;
-by 1: weight ratio (5-20) adds the dichloromethane solution of N-benzoyl-N '-p-hydroxybenzene thiocarbamide in poly acryloyl chloride, the concentration of the dichloromethane solution of described N-benzoyl-N '-p-hydroxybenzene thiocarbamide is 2-8%; Add pyridine and phase transfer catalyst again, the weight ratio of described pyridine and poly acryloyl chloride is (0.5-1.5): 1; The weight ratio of described phase transfer catalyst and pyridine is (0.01-0.5): 1; Stirring reaction backflow 30-40 hour then, filtration use washed with dichloromethane, and drying can obtain the end product water absorbing bond linkage polymer plant growth regulators in 75-85 ℃ of vacuum drying chamber.
Purpose of the present invention also can realize by following measure:
The preparation technology's of water absorbing bond linkage polymer plant growth regulators phase transfer catalyst can be selected from PEG-200 to PEG-1000, softex kw, benzyltrimethylammonium chloride.
The present invention has following advantage compared to existing technology:
1, the present invention is chemically bound in little molecule plant growth regulator N-benzoyl-N '-p-hydroxybenzene thiocarbamide on the water imbibition polyacrylic resin by active ester bond, can find out that according to sem photograph surface of the present invention is little column or little granular texture; And the structure of polyacrylic resin itself is netted, and the present invention is a kind of new macromolecular compound; Be particularly useful for the growth of arid area crops.
2, the present invention is because it is that little molecule plant growth regulator N-benzoyl-N '-p-hydroxybenzene thiocarbamide is chemically bound on the water imbibition polyacrylic resin by active ester bond, compound of the present invention need be hydrolyzed in the use, its little molecule plant growth regulator could decompose with polyacrylic resin, discharge from polyacrylic resin, its rate of release is slow again; And embedding type plant growth regulator of the prior art is because binding reaction does not take place itself only is with the embedding of little molecule plant growth regulator, thereby little molecule plant growth regulator can directly discharge from resin, and its rate of release is very fast; The contrast experiment of the present invention by the offspring of sowing after the wheat carried out, result's proof is along with the increase of sowing number of times, and long-lasting, slow release effect of the present invention is better than other class plant growth regulator.
3, technological process of the present invention is short, stable, reliable.
The present invention also will be described in further detail in conjunction with the embodiments:
Embodiment:
With cross linked sodium polyacrylate PAA
1Or PAA
2(the two water absorption rate is respectively 6g/g, 2g/g) becomes polyacrylic resin transition with 5% hydrochloric acid; press the listed raw material proportioning of table 1 and in container, add polyacrylic acid and thionyl chloride; the water-bath back flow reaction is 8.5 hours under the magnetic agitation; decompression distillation is removed excessive thionyl chloride and is got poly acryloyl chloride then; its molecular weight is 2000-5000, adds the dichloromethane solution of N-benzoyl-N '-p-hydroxybenzene thiocarbamide in poly acryloyl chloride.Its concentration is 5%, adds pyridine and phase transfer catalyst again, then stirring reaction backflow 35 hours, filtration.With washed with dichloromethane 3 times.Each consumption is 10 weight portions, and drying can obtain end product in 80 ℃ of vacuum drying chambers.Course of reaction of the present invention is as follows:
The diffuse reflectance infrared spectroscopy of plant growth regulator of the present invention sees Table 2, Fig. 1, and the PGR in Fig. 1, the table 2 is little molecule plant growth regulator N-benzoyl-N '-p-hydroxybenzene thiocarbamide, PAA
1-COCl is that water absorption rate is the cross linked sodium polyacrylate of 6g/g and the reactant poly acryloyl chloride of thionyl chloride, PAA
1-PGR is a binding type polymer plant growth conditioning agent of the present invention, PAA
2-COCl is that water absorption rate is the cross linked sodium polyacrylate of 2g/g and the reactant poly acryloyl chloride of thionyl chloride, PAA
2-PGR is a binding type polymer plant growth conditioning agent of the present invention.
The characteristic peak positions of table two compound
Fig. 1 uses KB
1The plant growth regulator that pressed disc method records (PGR), cross-linking type poly acryloyl chloride (PAA
1-COCl, PAA
2-COCl), binding type polymer plant growth conditioning agent (PAA
1-PGR, PAA
2-PGR) infrared spectrogram.
By table 2 and Fig. 1 as can be known, polymer plant growth conditioning agent PAA
1-PGR, PAA
2Among-the PGR, vc-cl weakens at the peak, has gone out the characteristic peak of plant growth regulator respectively, vc0 (PAA
1-PGR:1637cm
-1, PAA
2-PGR:1603cm
-1).Phenyl ring skeletal vibration peak (PAA
1-PGR:1540cm
-1, 1487cm
-1, PAA
2-PGR:1445cm
-1, 1550cm
-1).The phenyl ring list replaces characteristic peak (PAA
1-PGR:752cm
-1, PAA
2-PGR:756cm
-1).Phenyl ring contraposition two replaces characteristic peak (PAA
1-PGR:932cm
-1, PAA
2-PGR:904cm
-1But also ester carbonyl stretching vibration peak (PAA has appearred
1-PGR:15cm
-1, PAA
2-PGR:1703cm
-1) and ester C-O singly-bound stretching vibration peak (PAA
1-PGR:1234cm
-1, be a broad peak, PAA
2-PGR:1113cm
-1, be a broad peak).Red shift takes place and (moves about 100cm in the ester carbonyl group peak vo0 of polymer plant growth conditioning agent
-1-170cm
-1), reason is that the chlorine on the cross-linking type poly acryloyl chloride is replaced by the aryloxy group of plant growth substance, forms ester bond, because of the inductive effect of the aromatic ring inductive effect less than chlorine, so that the bond energy of the CO of polymer plant growth conditioning agent less than the bond energy of acyl chlorides CO, so vc0 wave number generation red shift.The C-O singly-bound stretching vibration peak of ester is at 1000-1300cm
-1The place is the last one and wide absworption peak, and the vN-CS vibration peak with this in interval is covered, and can't resolve.Because after plant biotechnology regulator and the reaction of cross-linking type poly acryloyl chloride, hydrogen on the plant growth regulator hydroxyl is replaced by polyacrylic carbonyl, according to inductive effect, make that cloud density reduces on the phenyl ring, and cloud density increases between phenyl ring and the substituting group, be that C-C key bond energy increases between phenyl ring and the substituting group, make to replace peak generation violet shift, phenyl ring skeleton stretching vibration peak generation red shift.
Claims (3)
1, a kind of water absorbing bond linkage polymer plant growth regulators is characterized in that structural formula is:
Its molecular weight is 2000-5000.
2, the preparation technology of the described water absorbing bond linkage polymer plant growth regulators of a kind of claim 1, it is poly-to it is characterized in that it contains the following step:
-in container, press 1: weight ratio (5-15) adds polyacrylic resin and thionyl chloride, and the water-bath back flow reaction is 7-10 hour under the magnetic agitation; Decompression distillation is removed excessive thionyl chloride and is got poly acryloyl chloride then, and its molecular weight is 2000-5000;
-by 1: weight ratio (5-20) adds the dichloromethane solution of N-benzoyl-N '-p-hydroxybenzene thiocarbamide in poly acryloyl chloride, the concentration of the dichloromethane solution of described N-benzoyl-N '-p-hydroxybenzene thiocarbamide is 2-8%; Add pyridine and phase transfer catalyst again, the weight ratio of described pyridine and poly acryloyl chloride is (0.5-1.5): 1; The weight ratio of phase transfer catalyst and pyridine is (0.01-0.5): 1; Stirring reaction backflow 30-40 hour then, filtration use washed with dichloromethane, and drying can obtain the end product water absorbing bond linkage polymer plant growth regulators in 75-85 ℃ of vacuum drying chamber.
3, the preparation technology of water absorbing bond linkage polymer plant growth regulators as claimed in claim 2 is characterized in that phase transfer catalyst can be selected from PEG-200 to PEG-1000, softex kw, benzyltrimethylammonium chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97101624A CN1064213C (en) | 1997-01-25 | 1997-01-25 | Water absorbing bond linkage polymer plant growth regulators and the preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97101624A CN1064213C (en) | 1997-01-25 | 1997-01-25 | Water absorbing bond linkage polymer plant growth regulators and the preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1162390A CN1162390A (en) | 1997-10-22 |
| CN1064213C true CN1064213C (en) | 2001-04-11 |
Family
ID=5165866
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97101624A Expired - Fee Related CN1064213C (en) | 1997-01-25 | 1997-01-25 | Water absorbing bond linkage polymer plant growth regulators and the preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1064213C (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02119A (en) * | 1988-11-10 | 1990-01-05 | Sumitomo Chem Co Ltd | Lithium aluminum hydride based asymmetric reducing agent |
| JPH0386803A (en) * | 1989-08-30 | 1991-04-11 | Nippon Kayaku Co Ltd | Plant growth regulator-containing water absorbing polymer preparation and its use |
| JP3086803B1 (en) * | 1999-04-15 | 2000-09-11 | 工業技術院長 | Triazacyclononane compounds with chiral substituents and their metal complexes |
-
1997
- 1997-01-25 CN CN97101624A patent/CN1064213C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02119A (en) * | 1988-11-10 | 1990-01-05 | Sumitomo Chem Co Ltd | Lithium aluminum hydride based asymmetric reducing agent |
| JPH0386803A (en) * | 1989-08-30 | 1991-04-11 | Nippon Kayaku Co Ltd | Plant growth regulator-containing water absorbing polymer preparation and its use |
| JP3086803B1 (en) * | 1999-04-15 | 2000-09-11 | 工業技術院長 | Triazacyclononane compounds with chiral substituents and their metal complexes |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1162390A (en) | 1997-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1308266C (en) | Amino acid organic fertilizer, its preparation method and use | |
| CN103951531B (en) | A kind of charcoal base water conservation control slow-release fertilizer and its preparation method and application | |
| CN101544523B (en) | Fertilizer with biological ferment and preparation method and use method thereof | |
| CN108264398A (en) | A kind of preparation method of bagasse base Slow release organic fertilizer | |
| CN101058522A (en) | Leaf surface fertilizer for composite amino acid chelate complex | |
| CN101899395A (en) | Screening and construction method for composite microbial system for rapidly degrading rice straw and composite microbial system | |
| CN109704858A (en) | A kind of method of temperate condition production alga fertilizer | |
| CN111499431A (en) | Preparation method of seaweed compound fertilizer | |
| CN106220325B (en) | A kind of water-fast degradable plant nutrition slow-release material and preparation method thereof | |
| CN108329086A (en) | A kind of garden seedling tree organic fertilizer | |
| CN105152760A (en) | Osmanthus fragrans culture medium and preparation method thereof | |
| CN105272420A (en) | Organic fertilizer containing blue algae and preparing method of organic fertilizer | |
| CN105198677A (en) | Selenium-rich biological organic fertilizer and preparation method thereof | |
| CN1064213C (en) | Water absorbing bond linkage polymer plant growth regulators and the preparation thereof | |
| CN1312982C (en) | Soilless cultivating medium produced by using hickory shell and its producing method | |
| CN108383587A (en) | A kind of preparation method of bagasse base slow-release compound fertilizer | |
| CN110028353A (en) | A kind of control release type chelating microbial manure and preparation method thereof | |
| CN100345801C (en) | Agricultural amino acid | |
| CN107955619A (en) | A kind of composite soil modifier and preparation method thereof | |
| CN109258386A (en) | A kind of organic active repairs soil and preparation method thereof | |
| CN1228360C (en) | One-step synthesis process of producing biodegradable high-hydroscopicity resin directly with corn powder | |
| CN1257958C (en) | Rare earth anti-drought water-loss reducer | |
| CN105175118B (en) | Improve the soil alkaline fertilizer special for banana material of diseases prevention and preparation method thereof | |
| CN107353163A (en) | A kind of agricultural water-loss reducer and preparation method thereof | |
| CN1098829C (en) | Prepn. method of pure natural multielement organic fertilizer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |