CN107353434A - A kind of preparation method using hydroxypropylation lobster shell as primary raw material composite water conservation material - Google Patents

A kind of preparation method using hydroxypropylation lobster shell as primary raw material composite water conservation material Download PDF

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Publication number
CN107353434A
CN107353434A CN201710572566.5A CN201710572566A CN107353434A CN 107353434 A CN107353434 A CN 107353434A CN 201710572566 A CN201710572566 A CN 201710572566A CN 107353434 A CN107353434 A CN 107353434A
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China
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weight
hydroxypropylation
water conservation
parts
primary raw
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CN201710572566.5A
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Inventor
王如峰
凌武海
王子舟
王宇渤
余红喜
任信林
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QUANJIAO CHIZHEN LOBSTER ECONOMIC PROFESSIONAL COOPERATION
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QUANJIAO CHIZHEN LOBSTER ECONOMIC PROFESSIONAL COOPERATION
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Priority to CN201710572566.5A priority Critical patent/CN107353434A/en
Publication of CN107353434A publication Critical patent/CN107353434A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/21—Urea; Derivatives thereof, e.g. biuret
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Fertilizers (AREA)

Abstract

The invention discloses a kind of preparation method using hydroxypropylation lobster shell as primary raw material composite water conservation material, first with lobster shell after high-pressure steam sterilizing pan carries out high-temperature process, it is then added in dilute hydrochloric acid solution and carries out boiling processing, ball milling is into fine powder, it is then dissolved in freezing processing after sodium hydroxide solution stirring and dissolving, thaw to be added in absolute ethyl alcohol again and add after tetramethyl ammonium hydroxide solution and expoxy propane reacted, add after the ultrasonic reactions such as egg-shell meal by processing both.The standby water-keeping material of the present invention has efficient water conservation moisture-keeping functions, and high absorption and slow releasing function, can carry out adsorption fertilizer and sustained release, improve utilization rate of fertilizer.

Description

A kind of preparation method using hydroxypropylation lobster shell as primary raw material composite water conservation material
Technical field
The invention belongs to water-keeping material technical field, and in particular to a kind of compound as primary raw material using hydroxypropylation lobster shell The preparation method of water-keeping material.
Background technology
China cray industry develops rapidly in recent years, while national material life is met, also generates substantial amounts of Discarded object using shrimp shell as representative.Chitin is natural high as obtained from shrimp, crab or insect shell pass through soda acid working process Molecular material, and chitosan is the derivative of chitin.
Chitin, also known as chitin, chitin, chitin etc., it is by 2-Acetamido-2-deoxy-D-glucose polycondensation The linear polymer formed.Its close crystal structure makes its not soluble in water, diluted acid, alkali, alcohol and other organic solvents.This Its application is limited to a certain extent.But its deacetylation product chitosan, due to adding active group-ammonia Base, its dissolubility is set to make moderate progress, application for chitin compared with also having obtained greatly promoting.Chitosan is in nature Unique alkaline polysaccharide, the content in nature are only second to cellulose.
Chitosan is a kind of polycation polysaccharide, is obtained by chitin through deacetylated, has good biocompatibility And degradability, have broad application prospects in terms of high-absorbent material is prepared.CS is cationic polymer, is contained on strand big The hydrophilic radical of amount, such as hydroxyl, amino, acetylamino, therefore can be prepared by carrying out the reaction of appropriateness with high water absorption The material of water retention property.
The content of the invention
The present invention provides a kind of preparation method using hydroxypropylation lobster shell as primary raw material composite water conservation material, preparation Water-keeping material has efficient water conservation moisture-keeping functions, and high absorption and slow releasing function, can carry out adsorption fertilizer and sustained release, improve Utilization rate of fertilizer.
The present invention is achieved by the following technical solutions：
A kind of preparation method using hydroxypropylation lobster shell as primary raw material composite water conservation material, comprise the following steps：
（1）20-30 parts by weight lobster shells are placed in high-pressure steam sterilizing pan 120-130 DEG C of temperature, insulation 5-15 minutes are set Afterwards, take out add 25-35 parts by weight 0.1-0.5mol/L watery hydrochloric acid boil cool down after 20-30 minutes after 3-4 is washed with water After secondary, dry, dried at a temperature of 105-115 DEG C, after ball mill ball milling 60-90 minutes, obtained stand-by after powder；
（2）By step（1）Gains are dissolved in 50-80 parts by weight 0.1-0.5mol/L sodium hydrate aqueous solutions, are stirred Afterwards, it is put into refrigerator and freezes 3-7 days, 20-30 parts by weight absolute ethyl alcohol is added after defrosting and carries out dissolving 30-60 minutes, is added 10-20 weight 10-20% tetramethyl ammonium hydroxide solutions, add the expoxy propane of 20-30 parts by weight, room while stirring at room temperature 1-3 hours are stirred under temperature, it is stand-by；
（3）By 10-20 parts by weight egg-shell meals, 2-7 parts by weight zeolite powders, 5-15 parts by weight of urea is added to step（2）Gains In, it is placed on ultrasonic cleaner, Ultrasonic Heating back flow reaction 1-6 hours, cools down after well mixed, filtering, filter cake is with anhydrous After ethanol washs 3-4 times, drying, it is primary raw material composite water conservation material to be both able to hydroxypropylation lobster shell.
The step（1）Ball mill it is levigate for charged ball grinder is fixed on ball mill with 200-300r/min Rotating speed ball milling 30-40 minutes, then ball grinder is removed, rocked 5-10 times up and down, ball grinder is then once again secured in ball On grinding machine, continue ball milling 20-60 minutes.
The step（2）Middle thaw is thawed for naturally to thaw at ambient temperature or be placed in microwave reactor.
Described ultrasonic reaction is that to set ultrasonic cleaner parameter be 50-60V, 65-75 DEG C of ultrasonic reaction temperature.
Described zeolite powder is 100-300 mesh.
It is an advantage of the invention that：
（1）The present invention after high-pressure steam sterilizing pan carries out high-temperature process, is then added to watery hydrochloric acid first with lobster shell Carry out boiling processing in solution, ball milling is then dissolved in freezing processing after sodium hydroxide solution stirring and dissolving, then solve into fine powder Jelly, which is added in absolute ethyl alcohol, to be added after tetramethyl ammonium hydroxide solution and expoxy propane reacted, and adds the ultrasounds such as egg-shell meal Both obtained by processing after reaction.Lobster shell passes through high-pressure steam sterilizing pan sterilization treatment, loose shrimp shell, and watery hydrochloric acid can accelerate dragon The rate of dissolution of protein, removes isolating protein in shrimp shell, sloughs part second phthalidyl, is added to freezing processing in sodium hydroxide afterwards After swelling, and sodium hydroxide can be bonded with hydroxyl, form activated centre, when hydroxypropylation reacts, activated centre and reactant Expoxy propane contacts, and nucleophilic substitution occurs, and generates hydroxypropyl based products, and ultrasonic wave accelerates synthesis rate, introduces hydrophilic group Carboxyl is rolled into a ball to improve water solubility.
（2）The standby water-keeping material of the present invention has efficient water conservation moisture-keeping functions, and high absorption and slow releasing function, Ke Yijin Row adsorption fertilizer and sustained release, improve utilization rate of fertilizer.
Embodiment
A kind of preparation method using hydroxypropylation lobster shell as primary raw material composite water conservation material, comprise the following steps：
（1）After being placed in 125 DEG C of temperature of setting in high-pressure steam sterilizing pan by 25 parts by weight lobster shells, be incubated 10 minutes, take out and add Enter 30 parts by weight 0.3mol/L watery hydrochloric acid to carry out after being washed with water 3 times after cooling down after boiling 25 minutes, dry, in 110 DEG C of temperature Lower drying, ball mill ball milling is after 75 minutes, obtains stand-by after powder；
（2）By step（1）Gains are dissolved in 65 parts by weight 0.3mol/L sodium hydrate aqueous solutions, after stirring, are put into Freezed 5 days in refrigerator, 25 parts by weight absolute ethyl alcohols are added after defrosting and carry out dissolving 45 minutes, add the tetramethyl of 15 weight 10% Ammonia, adds the expoxy propane of 25 parts by weight while stirring at room temperature, is stirred at room temperature 2 hours, stand-by；
（3）By 15 parts by weight egg-shell meals, 5 parts by weight zeolite powders, 10 parts by weight of urea are added to step（2）In gains, mixing It is placed on ultrasonic cleaner, Ultrasonic Heating back flow reaction 3 hours, cools down after uniformly, filtering, filter cake washs 3 with absolute ethyl alcohol After secondary, drying, it is primary raw material composite water conservation material to be both able to hydroxypropylation lobster shell.
The step（1）Ball mill it is levigate be by charged ball grinder be fixed on ball mill with 250r/min turn Fast ball milling 35 minutes, then removes ball grinder, rocks 8 times, ball grinder is once again secured on ball mill up and down then, continues Ball milling 40 minutes.
The step（2）Middle thaw is thawed for naturally to thaw at ambient temperature or be placed in microwave reactor.
Described ultrasonic reaction is that to set ultrasonic cleaner parameter be 55V, ultrasonic reaction temperature 70 C.
Described zeolite powder is 150 mesh.

Claims (5)

  1. A kind of 1. preparation method using hydroxypropylation lobster shell as primary raw material composite water conservation material, it is characterised in that including with Lower step：
    (1) 20-30 parts by weight lobster shells are placed in high-pressure steam sterilizing pan and 120-130 DEG C of temperature, insulation 5-15 minutes is set Afterwards, take out add 25-35 parts by weight 0.1-0.5mol/L watery hydrochloric acid boil cool down after 20-30 minutes after 3-4 is washed with water After secondary, dry, dried at a temperature of 105-115 DEG C, after ball mill ball milling 60-90 minutes, obtained stand-by after powder；
    (2) by step（1）Gains are dissolved in 50-80 parts by weight 0.1-0.5mol/L sodium hydrate aqueous solutions, are stirred Afterwards, it is put into refrigerator and freezes 3-7 days, 20-30 parts by weight absolute ethyl alcohol is added after defrosting and carries out dissolving 30-60 minutes, is added 10-20 weight 10-20% tetramethyl ammonium hydroxide solutions, add the expoxy propane of 20-30 parts by weight, room while stirring at room temperature 1-3 hours are stirred under temperature, it is stand-by；
    (3) 10-20 parts by weight egg-shell meals, 2-7 parts by weight zeolite powders, 5-15 parts by weight of urea are added to step（2）Gains In, it is placed on ultrasonic cleaner, Ultrasonic Heating back flow reaction 1-6 hours, cools down after well mixed, filtering, filter cake is with anhydrous After ethanol washs 3-4 times, drying, it is primary raw material composite water conservation material to be both able to hydroxypropylation lobster shell.
  2. A kind of 2. preparation side using hydroxypropylation lobster shell as primary raw material composite water conservation material according to claim 1 Method, the step（1）Ball mill it is levigate be by charged ball grinder be fixed on ball mill with 200-300r/min turn Fast ball milling 30-40 minutes, then ball grinder is removed, rocked 5-10 times up and down, ball grinder is then once again secured in ball mill On, continue ball milling 20-60 minutes.
  3. A kind of 3. preparation side using hydroxypropylation lobster shell as primary raw material composite water conservation material according to claim 1 Method, the step（2）Middle thaw is thawed for naturally to thaw at ambient temperature or be placed in microwave reactor.
  4. A kind of 4. preparation side using hydroxypropylation lobster shell as primary raw material composite water conservation material according to claim 1 Method, described ultrasonic reaction are that to set ultrasonic cleaner parameter be 50-60V, 65-75 DEG C of ultrasonic reaction temperature.
  5. A kind of 5. preparation side using hydroxypropylation lobster shell as primary raw material composite water conservation material according to claim 1 Method, described zeolite powder are 100-300 mesh.
CN201710572566.5A 2017-07-13 2017-07-13 A kind of preparation method using hydroxypropylation lobster shell as primary raw material composite water conservation material Pending CN107353434A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110724311A (en) * 2019-10-14 2020-01-24 浙江海洋大学 Method for preparing degradable packaging material by using euphausia superba shell
CN115316220A (en) * 2022-08-19 2022-11-11 潍坊峡兴农业科技有限公司 Preparation method of selenium-rich nutrient soil

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104072280A (en) * 2014-06-13 2014-10-01 平和三平绿源生物技术有限公司 Chitin active calcium fertilizer and preparation method thereof
CN105016879A (en) * 2015-07-23 2015-11-04 潘昌仁 Compound water retention efficiency-improving fertilizer
CN105906413A (en) * 2016-04-15 2016-08-31 陕西科技大学 Water-retaining chitosan bacteriostatic antibiotic fertilizer and preparation method thereof
CN106242712A (en) * 2016-06-13 2016-12-21 杭州罗壳素农业科技有限公司 A kind of preparation method of the novel nano fertilizer synergist with Crusta Penaeus seu Panulirus as raw material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104072280A (en) * 2014-06-13 2014-10-01 平和三平绿源生物技术有限公司 Chitin active calcium fertilizer and preparation method thereof
CN105016879A (en) * 2015-07-23 2015-11-04 潘昌仁 Compound water retention efficiency-improving fertilizer
CN105906413A (en) * 2016-04-15 2016-08-31 陕西科技大学 Water-retaining chitosan bacteriostatic antibiotic fertilizer and preparation method thereof
CN106242712A (en) * 2016-06-13 2016-12-21 杭州罗壳素农业科技有限公司 A kind of preparation method of the novel nano fertilizer synergist with Crusta Penaeus seu Panulirus as raw material

Non-Patent Citations (3)

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Title
施亦东: "《生态纺织品与环保染化助剂》", 28 February 2014, 中国纺织出版社 *
朱婉萍 等: "《甲壳素及其衍生物的研究与应用》", 30 November 2014, 浙江大学出版社 *
陈忻 等: "羟丙基壳聚糖的制备", 《合成化学》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110724311A (en) * 2019-10-14 2020-01-24 浙江海洋大学 Method for preparing degradable packaging material by using euphausia superba shell
CN115316220A (en) * 2022-08-19 2022-11-11 潍坊峡兴农业科技有限公司 Preparation method of selenium-rich nutrient soil
CN115316220B (en) * 2022-08-19 2024-04-05 潍坊峡兴农业科技有限公司 Preparation method of selenium-enriched nutrient soil

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