CN102226008A - Preparation method of material with high water absorbability - Google Patents

Preparation method of material with high water absorbability Download PDF

Info

Publication number
CN102226008A
CN102226008A CN2011101429523A CN201110142952A CN102226008A CN 102226008 A CN102226008 A CN 102226008A CN 2011101429523 A CN2011101429523 A CN 2011101429523A CN 201110142952 A CN201110142952 A CN 201110142952A CN 102226008 A CN102226008 A CN 102226008A
Authority
CN
China
Prior art keywords
preparation
acid
linking agent
high absorbency
absorbency material
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
Application number
CN2011101429523A
Other languages
Chinese (zh)
Inventor
陈煜�
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing Institute of Technology BIT
Original Assignee
Beijing Institute of Technology BIT
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Beijing Institute of Technology BIT filed Critical Beijing Institute of Technology BIT
Priority to CN2011101429523A priority Critical patent/CN102226008A/en
Publication of CN102226008A publication Critical patent/CN102226008A/en
Pending legal-status Critical Current

Links

Abstract

The invention relates to a preparation method of a material with high water absorbability, and belongs to the field of polymer material preparation. According to the method of the invention, a linear hydrophilic polymer is used as a raw material, is crosslinked with high-valent cations through polyelectrolyte compound effect to obtain a gel with high water absorbability; and the gel is further dried to prepare the material with high water absorbability. The preparation process of the method of the invention has less heat release, mild reaction conditions, and is suitable for the fixation and protection of the embedded substance; the material with high water absorbability prepared by the method of the invention has excellent water absorbability, and certain degradability, can be prepared into powder, sponginess, and patches, has a soft and smooth product surface, and is widely applicable to the fields of agriculture, medical materials, physiological hygienic materials, and the like.

Description

The preparation method of one class high absorbency material
Technical field
The present invention relates to the preparation method of a class high absorbency material, belong to macromolecule material preparation area.
Background technology
High absorbency material is owing to suction, the water retention property of its excellence, and the application in physiological hygiene articles for use, agriculture production, intelligent medicine controlled releasing and body fluid sorbing material in recent years receives publicity.
But the main method of high absorbency material preparation at present is the Raolical polymerizable by hydrophilic vinyl monomer, and crosslinked method prepares simultaneously.Though this method is the method for industrial a large amount of employings at present, has following problem:
1. the free radical solution polymerization method forms the gel of bulk easily in polymerization process, and polymerization process is emitted a large amount of heat simultaneously, the heat radiation difficulty of gel, and the reaction unit diameter is restricted; The condenser system that accessory is had relatively high expectations in the reaction unit has increased production cost.
Though 2. the reversed emulsion polymerization heat radiation easily, but need to use a large amount of organic solvents in the polymerization process, have certain environmental pollution, the existence of organic solvent has simultaneously also limited the abundant polymerization of vinyl monomer, has influenced the raising of polymericular weight and water absorbing properties.
3. in high absorbency material to medicine, microorganism, fertilizer, the equimolecular embedding of agricultural chemicals, be further to improve the functional important channel of high absorbency material.But owing to emit a large amount of heat in the above-mentioned polymerization process, easily to being produced certain destruction by the embedding molecule; In addition, normal peroxide or the oxidation-reduction trigger system that adopts in the polymerization process is also easily to being played certain oxidation destruction by the embedding thing.Therefore, embedding poor effect in polymerization process.But after the network of high absorbency material forms, be unfavorable for again being entered network internal, also influenced the embedding effect by the embedding thing.The problems referred to above have limited the functional modification of high absorbency material and have used.
4. high absorbency material prepares formed gel, and dry back is crisp and hard, just can use after it must being ground into powder.But, when high absorbency material contacts use as medical material with human body skin, mucous membrane etc., after expanding, pulverous material easily sticks in the surface of skin, mucous membrane, and cause and use the difficult defective of back cleaning.If can improve the film forming properties of high absorbency material, will expand the range of application of high absorbency material greatly.
Summary of the invention:
The objective of the invention is there is the production cost height when the poly-method of tradition prepares high absorbency material in order to solve, water absorbing properties is poor, the embedding effect is bad, use back cleaning difficulty, and certain problems such as environmental pollution are arranged, and a kind of preparation method of new high absorbency material is provided.The linear hydrophilic polymer of this method employing is a raw material, and is crosslinked by the polyelectrolyte compound action with high-valence cationic, form superabsorbent gels, and then further drying makes powdery, sponge or the membrane-like material with high-hydroscopicity energy.
The objective of the invention is to be achieved through the following technical solutions:
The preparation method of a class high absorbency material of the present invention, concrete grammar is as follows:
Under 10~90 ℃, be 0.1~10% to be dissolved in the water hydrophilic polymer with mass concentration, under 5 rev/mins~300 rev/mins stirring velocity, stir, make the hydrophilic polymer dissolving evenly; The pH value that adds acidity or basic cpd regulator solution then is 3~13, continues to stir 1~30 minute; Add the cross-linking agent aqueous solution that accounts for hydrophilic polymer solution quality 1~40% again, the mass concentration of linking agent is 1~50% in the cross-linking agent aqueous solution, stirs after 20 minutes~8 hours and makes superabsorbent gels; To make the finished product after the superabsorbent gels drying at last.
In above-mentioned preparation method, described hydrophilic polymer is the homopolymer of following a kind of monomer composition or the multipolymer that multiple monomer is formed: vinylformic acid, acrylamide, vinyl cyanide, vinyl pyrrolidone, 2-acrylamido-methyl propane sulfonic acid, vinyl sulfonic acid, esters of acrylic acid, vinyl alcohol; Be preferably the multipolymer of multipolymer, vinylformic acid and the vinyl pyrrolidone composition of polyacrylic acid, vinylformic acid and acrylamide composition, wherein acrylic acid units accounts for 30%~95% of copolymer quality content; The mass concentration that hydrophilic polymer is dissolved in the water is preferably 0.8~5%.
Described basic cpd is one or more the compound in sodium hydroxide, potassium hydroxide, sodium bicarbonate, the ammoniacal liquor, and being preferably sodium hydroxide, potassium hydroxide or sodium hydroxide and ammoniacal liquor is the compound of forming at 1: 1 with mol ratio.
Described acidic cpd is one or more the compound in hydrochloric acid, sulfuric acid, phosphoric acid, the lactic acid, and being preferably hydrochloric acid or hydrochloric acid and phosphoric acid is the compound of forming at 4: 1 with mol ratio.
The pH value of regulator solution is preferably 3.5~11.5 behind adding acidity or the basic cpd.
Described linking agent is the organic or inorganic salt of aluminium, iron, zirconium, chromium, titanium, or contains the quaternary ammonium salt of two above quaternary ammonium groups, is preferably aluminum chloride, Tai-Ace S 150, aluminium pillared montmorillonite, aluminum phosphate, polymerize aluminum chloride, iron(ic) chloride, ferric sulfate; The mass concentration of linking agent is preferably 10~25% in the described cross-linking agent aqueous solution, and it is 5~20% that cross-linking agent aqueous solution accounts for the polymers soln quality optimization.
Superabsorbent gels is carried out heat drying and pulverizes the back obtaining powdered product under 50~300 ℃;
Superabsorbent gels is carried out microwave drying and pulverizes the back obtaining powdered product under 10~200 ℃;
With superabsorbent gels is freezing freeze after, in-10~-70 ℃ freeze drier, can make membrane-like, spongy product after the freeze-drying, if also can obtain powdered product after will this spongy product pulverizing.
Beneficial effect
Method preparation process of the present invention heat release is little, need not adopt the strong initiator of oxidisability, and the reaction conditions gentleness is suitable for by the fixing of embedding thing and protection, thereby realizes by the slowly-releasing of embedding thing; Controlled to the hydrophilic macromolecule chain molecular weight, the preparation process mild condition, less demanding to the thermal diffusivity of reactor, without any need for organic solvent, be suitable for large-scale industrial production; Adopt the product of the inventive method preparation to have excellent water absorbing properties, also have certain degradable performance; Its water absorbent rate can reach 860 gram/grams, and the water absorbent rate in 0.9% physiological saline can reach 70 gram/grams; Remove and to be prepared into the powdered products beyond the region of objective existence, such high absorbency material also can be made into sponge, membrane-like, sponge, membrane-like product soft surface are smooth, and this class high absorbency material will have important use in fields such as agricultural, medical material and physiological hygiene materials and be worth.
Embodiment:
Below in conjunction with embodiment content of the present invention is described further:
Embodiment 1
Under 60 ℃, the multipolymer that 20 gram vinylformic acid and acrylamides are respectively accounted for massfraction 50% is dissolved into 1313 and restrains in the water, after stirring under 120 rev/mins the stirring velocity makes high molecular polymer dissolving evenly, after the pH value of adding sodium hydrate regulator solution is 8.5, continue to stir 15 minutes, and added 270 gram mass concentration and be 18% aluminum chloride aqueous solution; Under 60 ℃, make superabsorbent gels to continue stirring under 120 rev/mins the stirring velocity after 2 hours, product after the drying, is pulverized and made the powdery high absorbency material in 120 ℃ baking oven.
Embodiment 2
Under 70 ℃, is that the high-molecular copolymer of forming at 7: 3 is dissolved in the 980 gram water with 20 gram vinylformic acid and vinyl pyrrolidone with mass ratio, after stirring under 100 rev/mins the stirring velocity makes high molecular polymer dissolving evenly, adding hydrochloric acid and phosphoric acid is after the pH value of the compound regulator solution of 4: 1 compositions is 3.8 with mol ratio, continue to stir 20 minutes, add 204 gram mass concentration and be 15% the linking agent polymerize aluminum chloride aqueous solution; Under 70 ℃, make superabsorbent gels after 3 hours to continue stirring under 100 rev/mins the stirring velocity.Gel is freezed the back in-65 ℃ freeze drier, make spongy product after the drying.
Embodiment 3
Under 60 ℃, 20 gram polyacrylic acid are dissolved in the 1313 gram water, after stirring under 100 rev/mins the stirring velocity makes high molecular polymer dissolving evenly, after the pH value of adding acetic acid regulator solution is 3.8, continue to stir 15 minutes, and after further stirring 15 minutes, add 203 gram mass concentration and be 30% linking agent aluminium phosphate aqueous solution; Under 60 ℃, make superabsorbent gels after 4 hours to continue stirring under 100 rev/mins the stirring velocity.Gel is freezed the back in-65 ℃ freeze drier, make spongy product after the drying.
Embodiment 4
Under 75 ℃, is that the multipolymer that obtains at 7: 3 is dissolved in the 980 gram water with 20 gram vinylformic acid and 2-acrylamido-methyl propane sulfonic acid with mass ratio, after stirring under 150 rev/mins the stirring velocity makes high molecular polymer dissolving evenly, the pH value that adds the ammoniacal liquor regulator solution is after 80s, continue to stir 15 minutes, and added 300 gram mass concentration and be 20% ferric chloride in aqueous solution; Under 75 ℃, make superabsorbent gels to continue stirring under 150 rev/mins the stirring velocity after 3 hours, product is freezed back freeze-drying in-65 ℃ freeze drier make membranaceous product.
The absorbent test of the high absorbency material that the present invention is prepared:
Take by weighing the high absorbency material of 0.20 gram, place to put into behind the nylon cloth bag to fill the beaker that absorbs liquid, at room temperature fully swelling is removed the liquid on cloth bag surface, the quality of material after the weighing imbibition after 10 minutes.Liquid absorbency rate Q calculates by following formula:
Q = m 2 - m 1 m 1
In the formula, Q-liquid absorbency rate, gram/gram; m 1The quality of high absorbency material before the-imbibition, gram; m 2The quality of high absorbency material after the-imbibition, gram.
The water absorbent rate of the high absorbency material that embodiment 1 obtains reaches 810 gram/grams, inhales the physiological saline multiplying power and reaches 62 gram/grams.The water absorbent rate of the high-hydroscopicity sponge that embodiment 2 obtains reaches 860 gram/grams, inhales the physiological saline multiplying power and reaches 70 gram/grams.The water absorbent rate of the high-hydroscopicity sponge that embodiment 3 obtains reaches 752 gram/grams, inhales the physiological saline multiplying power and reaches 68 gram/grams.The water absorbent rate of the high-hydroscopicity film that embodiment 4 obtains reaches 730 gram/grams, inhales the physiological saline multiplying power and reaches 59 gram/grams.Polyvinylalcohol sponge water absorbent rate to clinical use is 110 gram/grams, and inhaling the physiological saline multiplying power is 51 gram/grams.

Claims (7)

1. the preparation method of a class high absorbency material is characterized in that concrete grammar is as follows:
Under 10~90 ℃, be 0.1~10% to be dissolved in the water hydrophilic polymer with mass concentration, under 5 rev/mins~300 rev/mins stirring velocity, stir, make the hydrophilic polymer dissolving evenly; The pH value that adds acidity or basic cpd regulator solution then is 3~13, continues under the same rotational speed to stir 1~30 minute; Add the cross-linking agent aqueous solution that accounts for hydrophilic polymer solution quality 1~40% again, the mass concentration of linking agent is 1~50% in the cross-linking agent aqueous solution, stirs after 20 minutes~8 hours under the same rotational speed and makes superabsorbent gels; To make the finished product after the superabsorbent gels drying at last;
Wherein, described hydrophilic polymer is the homopolymer of following a kind of monomer composition or the multipolymer that multiple monomer is formed: vinylformic acid, acrylamide, vinyl cyanide, vinyl pyrrolidone, 2-acrylamido-methyl propane sulfonic acid, vinyl sulfonic acid, esters of acrylic acid, vinyl alcohol;
Described basic cpd is one or more the compound in sodium hydroxide, potassium hydroxide, sodium bicarbonate, the ammoniacal liquor;
Described acidic cpd is one or more the compound in hydrochloric acid, sulfuric acid, phosphoric acid, the lactic acid;
Described linking agent is the organic or inorganic salt of aluminium, iron, zirconium, chromium, titanium, or contains the quaternary ammonium salt of two above quaternary ammonium groups.
2. the preparation method of a class high absorbency material as claimed in claim 1, it is characterized in that: described hydrophilic polymer is preferably the multipolymer of multipolymer, vinylformic acid and the vinyl pyrrolidone composition of polyacrylic acid, vinylformic acid and acrylamide composition, wherein, acrylic acid units accounts for 30%~95% of copolymer quality content; The mass concentration that hydrophilic polymer is dissolved in the water is preferably 0.8~5%.
3. the preparation method of a class high absorbency material as claimed in claim 1 is characterized in that: described basic cpd is preferably sodium hydroxide, potassium hydroxide or sodium hydroxide and ammoniacal liquor is the compound of forming at 1: 1 with mol ratio.
4. the preparation method of a class high absorbency material as claimed in claim 1 is characterized in that: it is the compound of forming at 4: 1 with mol ratio that described acidic cpd is preferably hydrochloric acid or hydrochloric acid and phosphoric acid.
5. the preparation method of a class high absorbency material as claimed in claim 1 is characterized in that: the pH value of regulator solution is preferably 3.5~11.5 behind adding acidity or the basic cpd.
6. the preparation method of a class high absorbency material as claimed in claim 1 is characterized in that: described linking agent is preferably aluminum chloride, Tai-Ace S 150, aluminium pillared montmorillonite, aluminum phosphate, polymerize aluminum chloride, iron(ic) chloride, ferric sulfate; The mass concentration of linking agent is preferably 10~25% in the cross-linking agent aqueous solution, and it is 5~20% that cross-linking agent aqueous solution accounts for the polymers soln quality optimization.
7. the preparation method of a class high absorbency material as claimed in claim 1 is characterized in that: described superabsorbent gels adopts different drying conditionss can make Powdered, sponge, membrane-like material.
CN2011101429523A 2011-05-30 2011-05-30 Preparation method of material with high water absorbability Pending CN102226008A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2011101429523A CN102226008A (en) 2011-05-30 2011-05-30 Preparation method of material with high water absorbability

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2011101429523A CN102226008A (en) 2011-05-30 2011-05-30 Preparation method of material with high water absorbability

Publications (1)

Publication Number Publication Date
CN102226008A true CN102226008A (en) 2011-10-26

Family

ID=44807009

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2011101429523A Pending CN102226008A (en) 2011-05-30 2011-05-30 Preparation method of material with high water absorbability

Country Status (1)

Country Link
CN (1) CN102226008A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104446846A (en) * 2013-09-12 2015-03-25 仲恺农业工程学院 Water -absorbing water-retention slow and controlled release fertilizer preparation method
CN105061961A (en) * 2015-08-26 2015-11-18 北京理工大学 Salt tolerance super water-absorbent resin
CN113480755A (en) * 2021-07-19 2021-10-08 浙江大学 Method for enhancing polyelectrolyte hydrogel through metal ion in-situ coordination

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5115011A (en) * 1989-02-28 1992-05-19 Nippon Shokubai Kagaku Kogyo Co., Ltd. Process for producing quality-improved water-absorbent polymers and products
CN101519496A (en) * 2009-03-31 2009-09-02 山东大学 Method for preparing high water absorbent

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5115011A (en) * 1989-02-28 1992-05-19 Nippon Shokubai Kagaku Kogyo Co., Ltd. Process for producing quality-improved water-absorbent polymers and products
CN101519496A (en) * 2009-03-31 2009-09-02 山东大学 Method for preparing high water absorbent

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
《Iranian Polymer Journal》 20101231 Yu Chen等 "A Sustained Release of Model Drug from a Novel Polyacrylic Acid-polyaluminium Chloride Superabsorbent" 第19卷, 第7期 *
YU CHEN等: ""A Sustained Release of Model Drug from a Novel Polyacrylic Acid-polyaluminium Chloride Superabsorbent"", 《IRANIAN POLYMER JOURNAL》 *
YU CHEN等: ""A Sustained Release of Model Drug from a Novel Polyacrylic Acid-polyaluminium Chloride Superabsorbent"", 《IRANIAN POLYMER JOURNAL》, vol. 19, no. 7, 31 December 2010 (2010-12-31) *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104446846A (en) * 2013-09-12 2015-03-25 仲恺农业工程学院 Water -absorbing water-retention slow and controlled release fertilizer preparation method
CN105061961A (en) * 2015-08-26 2015-11-18 北京理工大学 Salt tolerance super water-absorbent resin
CN113480755A (en) * 2021-07-19 2021-10-08 浙江大学 Method for enhancing polyelectrolyte hydrogel through metal ion in-situ coordination

Similar Documents

Publication Publication Date Title
CN101914213B (en) Synthetic method of anti-compression and anti-bacterial super absorbent polymer for physiology
Chen et al. Synthesis and modification of salt-resistant superabsorbent polymers
CN103910896B (en) A kind ofly lowly return the preparation method of oozing hydroscopic high-molecular resin
CN103920180B (en) A kind of antiseptic dressing aquagel and preparation method thereof
CN103588924B (en) Tea polyphenol-acrylic acid series super absorbent resin and preparation method thereof
CN100575374C (en) A kind of preparation method of acrylic acid series semi-interpenetration network composite high water absorption resin
CN101280044B (en) Biodegradable agricultural high-absorbent resin and preparation thereof
CN105061961B (en) A kind of salt-tolerant super absorbent polymer
RU2001126352A (en) Powdered, crosslinked, absorbent polymers, method for their preparation and their use
CN103665411A (en) High salt tolerance and high water absorption rate super absorbent resin and preparation method thereof
CN101935380B (en) Method for preparing potassium- and nitrogen-containing high water-absorbent resin from carboxymethyl potato starch serving as raw material
CN103102443B (en) A kind of synthesis of physiological hygiene hydroscopic high-molecular resin
CN104987461A (en) Chitosan derivative antibacterial superabsorbent gel and preparation method therefor
Qi et al. Water absorbency of super absorbent polymer based on flexible polymeric network
CN103554332A (en) Preparation method of salt-tolerant super absorbent resin
CN110184814A (en) A kind of medical antibacterial dressing and preparation method thereof
CN111675815A (en) Preparation method of antibacterial super absorbent resin
CN102226008A (en) Preparation method of material with high water absorbability
CN105175757A (en) Preparation method of salt-resistant super absorbent polymers
CN105561370A (en) Novel hemostatic material and preparation method thereof
CN103937139B (en) The preparation method of poly-(acrylic acid-vinylacetate)-polyethylene alcohol interpenetrating network super absorbent resin
CN103224630A (en) Method for preparing water-absorbing resin by ultraviolet and gamma-ray radiation ionization technique
CN107501547A (en) A kind of phenyl boric acid functionalization amphion block copolymer and glucose-sensitive bionic nano carrier
CN104725548A (en) Hydrogel as well as preparation method and application thereof
CN1239535C (en) Method for making water-absorbent acrylate resin

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20111026