CN112175167B - Odor-inhibiting hydrophilic soft sponge based on silicoaluminophosphate zeolite molecular sieve and preparation method thereof - Google Patents

Odor-inhibiting hydrophilic soft sponge based on silicoaluminophosphate zeolite molecular sieve and preparation method thereof Download PDF

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CN112175167B
CN112175167B CN202011004023.1A CN202011004023A CN112175167B CN 112175167 B CN112175167 B CN 112175167B CN 202011004023 A CN202011004023 A CN 202011004023A CN 112175167 B CN112175167 B CN 112175167B
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parts
molecular sieve
zeolite molecular
soft sponge
phosphorus
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CN112175167A (en
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翁文伟
祝二斌
吴晓彪
罗梅芳
戴飞
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Fujian Hengan Hygiene Material Co ltd
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Fujian Hengan Hygiene Material Co ltd
Hengan Fujian Holding Group Co Ltd
Fujian Hengan Household Life Article Co Ltd
Hengan China Hygiene Products Co Ltd
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/15203—Properties of the article, e.g. stiffness or absorbency
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/15577—Apparatus or processes for manufacturing
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/53—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • C08G18/40—High-molecular-weight compounds
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    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
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    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
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    • 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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    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/15203—Properties of the article, e.g. stiffness or absorbency
    • A61F2013/15284—Properties of the article, e.g. stiffness or absorbency characterized by quantifiable properties
    • A61F2013/15544—Permeability
    • A61F2013/1556—Water permeability
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/53—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium
    • A61F2013/530481—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium having superabsorbent materials, i.e. highly absorbent polymer gel materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/53—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium
    • A61F2013/530481—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium having superabsorbent materials, i.e. highly absorbent polymer gel materials
    • A61F2013/530583—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium having superabsorbent materials, i.e. highly absorbent polymer gel materials characterized by the form
    • A61F2013/530649—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium having superabsorbent materials, i.e. highly absorbent polymer gel materials characterized by the form in sponge or foam
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Abstract

The invention relates to a taste-inhibiting hydrophilic soft sponge based on a silicoaluminophosphate zeolite molecular sieve and a preparation method thereof, wherein the taste-inhibiting hydrophilic soft sponge is prepared from the following raw materials in parts by weight: 10.9 parts of DEP-505S, 9.1 parts of universal polyether polyol, 10 parts of toluene diisocyanate, 5 parts of dichloromethane, 0.5 part of organic silicone oil, 0.1 part of dimethylethanolamine, 0.1 part of stannous octoate, 5 parts of cellulose, 1 part of super absorbent resin and 1.5 parts of deionized water; 1 part of silicon-phosphorus-aluminum zeolite molecular sieve, the granularity of which is 0.5um, and the specific surface area of which is 750m2Per g, acidification and surface treatment according to the following processSurface coupling coating treatment: the method comprises the steps of putting a silicon-phosphorus-aluminum zeolite molecular sieve into a citric acid microcapsule solution to enable the concentration of the silicon-phosphorus-aluminum zeolite molecular sieve to be 5% -20%, performing ultrasonic treatment for 4-6 hours, performing suction filtration and drying to constant weight, and performing surface coupling coating treatment by using a silane coupling agent containing vinyl.

Description

Odor-inhibiting hydrophilic soft sponge based on silicoaluminophosphate zeolite molecular sieve and preparation method thereof
The application is application number: 201711422633.1, filing date: 12 and 25 in 2017, the invention name is: a hydrophilic soft sponge, a preparation method thereof and divisional application of the application thereof.
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a taste-inhibiting hydrophilic soft sponge based on a silicon-phosphorus-aluminum zeolite molecular sieve and a preparation method thereof.
Background
With the improvement of living standard and the development of sanitary material technology, disposable sanitary products are widely applied in nursing women and children. The disposable sanitary product comprises products such as sanitary towels, paper diapers, sanitary pads and the like, and the common characteristic of the products is that the products are provided with three main functional layers, namely a surface layer which can be penetrated by body fluid, an absorption core layer which has absorption and storage capacity to the body fluid and a bottom layer which can prevent the body fluid from leaking. The surface layer is generally made of non-woven fabric or perforated film material, the bottom layer is made of polyethylene film or composite material of polyethylene film and non-woven fabric, and the absorption core layer is mainly composed of multi-layer composite core body filled with super absorbent resin (SAP resin) or absorption core body formed by mixing fluff pulp and super absorbent resin.
However, the SAP absorbs several tens or even several hundreds of times of its own weight of liquid to form a gel having high water absorption and retention properties without squeezing out water absorbed in the gel even under a certain pressure. Therefore, the SAP is used as a carrier for absorbing body fluid in the disposable absorbent core body to replace or partially replace the absorption performance of fluff pulp, the thickness of the absorbent core layer is greatly reduced, the disposable sanitary product is developed towards the direction of light weight, ultra-thinning and ultra-breathability, and meanwhile, the phenomenon of back seepage caused by the fact that the body fluid in the absorbent core body returns to the surface layer again is effectively avoided, so that a user feels comfortable and dry. Accordingly, the use of SAPs in hygiene products is becoming more and more widespread. On the other hand, SAP also has its drawbacks in use. When the absorbent is used as a main absorbent of a core layer material, the SAP is often dispersed in the form of independent particles and is mixed in a fiber web of a fluffy non-woven fabric or fluff pulp fibers, the volume of the SAP particles can be rapidly expanded after the SAP particles absorb liquid, the gel is adhered to form pasty gel blocks, the relative position of the gel in a sanitary product can be displaced in the walking process of a user, the gel is agglomerated, and the sanitary product is easy to deform. The deformed sanitary product has reduced performance of absorbing and maintaining body fluid for many times, and is easy to cause side leakage and leakage of body fluid.
Based on the technical problems of the prior absorbing core body, the invention patent with the publication number of CN 102793610A discloses a high polymer material layer with water absorption and a sanitary product with water absorption, wherein the invention comprises a high polymer foaming framework and a high water absorption resin; the polymer foaming framework is prepared by a physical or chemical foaming method, the specific pore volume of the open pore structure is 5-200mL/g, and the opening rate is 50-100%; the high-water-absorption resin is adhered or embedded on the hole wall of the open pore structure, and each cubic meter of the high-polymer material layer contains 2-200kg of the high-water-absorption resin; and the water retention capacity of the high polymer material layer is not less than 5 g/g. The high-molecular foaming framework (10) is made of any one of foaming polyurethane, foaming EVA and foaming PE materials. After the scheme is adopted, as the super absorbent resin is adhered and embedded on the hole wall of the high molecular foaming framework, the super absorbent resin swells and locks body fluid when contacting body fluid. When a user walks, the super absorbent resin can not generate relative displacement in the sanitary product, thereby reducing the deformation of the sanitary product to the maximum extent and avoiding the agglomeration of the gel after absorbing the liquid.
However, in the polymer material layer or the hydrophilic sponge having water absorption in the prior art, the super absorbent resin is filled in the polyurethane resin body, so that the water absorption and water locking performance of the polyurethane are improved, and absorbed liquid is not easy to release, but the existing hydrophilic sponge has the technical problem of slow absorption speed due to insufficient hydrophilicity, and also has the problem of insufficient flexibility or/and resilience, so that when the existing hydrophilic sponge is used as an absorption core body of a disposable sanitary product, on one hand, the absorption rate is slow, and the phenomena of permeation and side leakage are caused, on the other hand, the insufficient resilience can greatly reduce the pressure-resistant absorption performance of the super absorbent resin, especially, when an infant is in a sitting posture or a sleeping posture, the pore structure of the polyurethane is collapsed under the pressure of the hydrophilic sponge, and the pressure is applied to the super absorbent resin, so that the absorption performance of the super absorbent resin is greatly reduced, the gel that exists in the same traditional absorption core blocks up the problem, and simultaneously, the softness is not enough will cause disposable hygienic products's the experience of wearing and comfort to descend, seriously influences the quality of goods.
Disclosure of Invention
The invention aims to provide a hydrophilic soft sponge aiming at the technical problems of low absorption speed caused by insufficient hydrophilicity and insufficient softness or/and rebound resilience of the existing hydrophilic sponge, and the hydrophilic soft sponge is improved in hydrophilicity and softness, and absorption performance, particularly pressure absorption performance, liquid permeability, diffusion permeability and deodorization function.
In order to achieve the purpose, the invention adopts the technical scheme that: the hydrophilic soft sponge has a developed and mutually communicated pore structure and a polyurethane skeleton structure connected with the pore structure, and super absorbent resin is combined in the polyurethane skeleton structure; the hydrophilic soft sponge is prepared from the following raw materials in parts by weight: 20-60 parts of polyether polyol, 10-40 parts of toluene diisocyanate, 5-15 parts of dichloromethane, 0.5-1.5 parts of organic silicone oil, 0.1-0.5 part of dimethylethanolamine, 0.1-0.5 part of stannous octoate, 5-15 parts of cellulose, 1-20 parts of super absorbent resin and 1.5-3 parts of deionized water.
Further comprises 1-15 parts of porous adsorption powder subjected to surface coupling coating treatment. The porous adsorption powder is at least one of zeolite molecular sieve, silica gel powder and montmorillonite powder, the particle size of the porous adsorption powder is 0.3-15um, and the specific surface area is 300-1200m2/g。
Further, before the surface coupling coating treatment, the porous adsorption powder is subjected to acidification treatment, and the coupling agent is one of a silane coupling agent containing vinyl, a silane coupling agent containing amino and a silane coupling agent containing epoxy.
Further, the detergent also comprises 0.5-4.5 parts of nonionic surfactant, wherein the nonionic surfactant is one or a combination of more than two of alkylphenol polyoxyethylene ether, lauryl alcohol polyoxyethylene ether, isomeric tridecanol ether, secondary alcohol polyoxyethylene ether, octanol polyoxyethylene ether, fatty acid methyl ester polyoxyethylene ether, linear chain deca-alcohol polyoxyethylene ether, linear chain octa-carbon isooctanol polyoxyethylene ether and polyoxyethylene sorbitan tristearate.
Further, the polyether polyol is EO-PO copolymerized polyether polyol and general polyether polyol according to the proportion of 1-2.5: 1, preferably 1.5: 1. The amount of ethylene oxide is 40-80% of the EO-PO copolymerized polyether polyol. Wherein the functionality of the EO-PO copolymerized polyether polyol is 2-3, and the molecular weight is 3200-3600.
The sponge has the advantages that the EO-PO copolymerized polyether polyol has high EO content, the hydrophilic performance of the sponge is improved, the polyether polyol with high EO content has high hydrophilic performance and softness, the general polyether polyol is added, the sponge has certain resilience, the synergistic effect of the polyether polyol with high EO content and the general polyether polyol is fully exerted, and the hydrophilic soft sponge with excellent hydrophilicity, softness and resilience is obtained.
According to the invention, polyether polyol is adopted to be matched with cellulose, so that the hydrophilicity of the sponge is further improved, the polyether polyol has higher activity, and the prepared hydrophilic soft sponge has excellent mechanical properties.
Further, the super absorbent resin is a granular polyacrylic acid series super absorbent resin, and the particle size range is 200-. As the super absorbent resin belongs to the polymer electrolyte, the water absorption capacity is contributed by hydrophilic groups (carboxyl and the like) in the super absorbent resin, the contact area of the granular super absorbent resin and water is large, the distance of water permeating from the surface to the inside is short, a polymer chain can be greatly extended, a three-dimensional network structure is large, the elastic contraction capacity of the three-dimensional network structure is reduced, more free water is contained, the water absorption speed is high, the water absorption capacity is large, and the occurrence of a dough phenomenon can be avoided.
The invention further provides a preparation method of the hydrophilic soft sponge, which comprises the following steps:
s1, weighing the raw materials in parts by weight respectively.
S2, putting polyether polyol, cellulose, porous adsorption powder, a non-ionic surfactant, super absorbent resin and deionized water into a storage vat, setting a constant material temperature at 20-23 ℃, and continuously stirring at a rotation speed of 15-120 r/min for 10-60min to obtain a material A.
S3, uniformly mixing toluene diisocyanate, dimethylethanolamine, stannous octoate, organic silicone oil and dichloromethane, and preheating the material to 20-23 ℃ to obtain a material B.
And S4, conveying the material A and the material B to a high-speed mixer in proportion for high-speed stirring and mixing, and then conveying to an overflow groove for foaming to obtain the hydrophilic soft sponge.
The invention also provides application of the hydrophilic soft sponge in the field of disposable absorbent articles. The disposable absorption product comprises a liquid-permeable top layer, a liquid-impermeable bottom layer and an absorption layer positioned between the liquid-permeable top layer and the liquid-impermeable bottom layer, wherein the absorption layer adopts the hydrophilic soft sponge.
The invention has the following beneficial technical effects:
the invention adopts polyether polyol with high EO content, general polyether polyol and cellulose for compounding, fully utilizes the polyether polyol with high EO content and high EO content which has higher hydrophilic performance and softness performance to products, simultaneously cooperates with the cellulose to further improve the hydrophilicity, so that the polyether polyol has higher hydrophilic activity, and the general polyether polyol with good indentation hardness to the products to obtain good rebound resilience, fully exerts the synergistic effect of the polyether polyol with high EO content and the general polyether polyol, on one hand, the sponge has certain hydrophilic performance, the hydrophilic performance and the good softness, on the other hand, the sponge has better rebound resilience, and the obtained hydrophilic soft sponge has excellent hydrophilicity, softness and rebound resilience, thereby endowing the hydrophilic soft sponge with high water absorption rate, High water absorbing speed, high water retaining capacity, high water absorbing capacity, less dewatering and high water retaining performance.
According to the invention, porous adsorption powder subjected to acidification pretreatment is added into a raw material formula for preparing the hydrophilic sponge, so that the hydrophilic sponge can adsorb and neutralize alkaline substances such as ammonia. Therefore, the deodorant has the beneficial technical effects that the deodorant is applied to disposable hygienic products, and has the advantages of ammonia gas adsorption, peculiar smell elimination and the like.
The preparation method of the hydrophilic soft sponge is simple and easy to implement, low in cost and beneficial to industrial production, and the hydrophilic soft sponge has the advantages of strong water absorption capacity, long shelf life and the like, can quickly absorb secretions of a human body, and has wide application prospects in the field of disposable sanitary products.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The term "EO": ethylene oxide (EO for short); "PO" refers to Propylene Oxide (PO).
The polyether polyol is EO-PO (ethylene oxide-propylene oxide) copolymer polyether polyol and general polyether polyol according to the proportion of 1-2.5: 1, in a specific embodiment, the ratio is preferably 1.2 to 1.8:1, and more preferably 1.5: 1. In a specific embodiment, the amount of ethylene oxide is 40-80% of the EO-PO copolymerized polyether polyol, which has a functionality of 2-3 and a molecular weight of 3200-3600.
The EO-PO copolymeric polyether polyol described herein is preferably DEP-505S (manufactured by Zibode chemical industries, Ltd.), having a functionality of 3 and a molecular weight of 3300.
The porous adsorption powder is at least one of zeolite molecular sieve, silica gel powder and montmorillonite powder, the granularity of the porous adsorption powder is 0.3-15um, and the specific surface area is 300-2(ii) in terms of/g. Zeolite molecular sieves are a class of aluminosilicate crystals having a regular microporous structure which not only possess the inherent physicochemical characteristics of common inorganic materials, but are also superior in that they are uniformly regular with a particular spatial orientationThe zeolite molecular sieve has the characteristics of sieving, shape-selective function and adjustable surface characteristics due to the characteristics of a crystal pore channel system, adjustable framework Si/Al ratio and the like. The zeolite molecular sieve is a material in the prior art, such as a silicon-aluminum zeolite molecular sieve, a silicon-phosphorus-aluminum zeolite molecular sieve or a POFs material. POFs materials are organic-inorganic hybrid framework materials connected by covalent bonds, wherein a monomer is formed by Si-O octahedra connected by benzene rings, and the monomer is polymerized by para-position of benzene. The silica gel powder is an adsorption material with rich microporous structure, high purity, high activity and high specific surface area, and the silica gel powder has adsorption performance due to the developed microporous structure and the inner hole surface.
As a further preferred embodiment, the porous adsorption powder is subjected to acidification treatment before surface coupling coating treatment, and the process method comprises the following steps: putting porous adsorption powder (such as a silicon-phosphorus-aluminum zeolite molecular sieve) into a citric acid microcapsule solution to ensure that the concentration of the porous adsorption powder (such as the silicon-phosphorus-aluminum zeolite molecular sieve) is 5-20%, then performing ultrasonic treatment for 4-6 hours, performing suction filtration, and drying at 40-45 ℃ to constant weight. And then adopting coupling agents, such as silane coupling agents containing vinyl, silane coupling agents containing amino and silane coupling agents containing epoxy groups to carry out coupling coating treatment on the surface of the porous adsorption powder. Among them, citric acid microcapsules are commercially available.
The super absorbent resin is a novel high polymer material, can absorb water which is hundreds of times to thousands of times of the self weight, and is non-toxic, harmless and pollution-free; has strong water absorption capacity and high water retention capacity. The super absorbent resin includes starch series, cellulose series and synthetic resin series, and the synthetic resin series includes polyacrylate, polyvinyl alcohol, polyacrylamide and the like. The super absorbent resin is preferably polyacrylate super absorbent resin with the particle size range of 200-410 mu m, and the super absorbent resin is polymerized by acrylic acid/sodium acrylate. The polyacrylic acid-based super absorbent resin of the present invention is commercially available.
The present invention will be further specifically described below with reference to examples.
Example 1
The hydrophilic soft sponge of the embodiment is prepared from the following raw materials in parts by weight: 10.9 parts of DEP-505S, 9.1 parts of universal polyether polyol, 10 parts of toluene diisocyanate, 5 parts of dichloromethane, 0.5 part of organic silicone oil, 0.1 part of dimethylethanolamine, 0.1 part of stannous octoate, 5 parts of cellulose, 1 part of super absorbent resin and 1.5 parts of deionized water. Wherein the super absorbent resin is polyacrylic acid super absorbent resin with the particle size of 200-410 mu m.
The preparation method of the hydrophilic soft sponge comprises the following steps:
s1, weighing the raw materials in parts by weight respectively.
S2, adding DEP-505S, universal polyether polyol, cellulose, super absorbent resin and deionized water into a storage vat, setting a constant material temperature of 20-23 ℃, and continuously stirring for 60min at a rotation speed of 15r/min to obtain a material A.
S3, uniformly mixing toluene diisocyanate, dimethylethanolamine, stannous octoate, organic silicone oil and dichloromethane, and preheating the material to 20-23 ℃ to obtain a material B.
And S4, conveying the material A and the material B to a high-speed mixer in proportion for high-speed stirring and mixing, and then conveying to an overflow groove for foaming to obtain the hydrophilic soft sponge.
The hydrophilic soft sponge of the present embodiment has a developed and interconnected pore structure and a polyurethane skeleton structure connecting the pore structures, and a super absorbent resin is bonded in the polyurethane skeleton structure.
Example 2
The hydrophilic soft sponge of the embodiment is prepared from the following raw materials in parts by weight: 36 parts of DEP-505S, 24 parts of universal polyether polyol, 40 parts of toluene diisocyanate, 15 parts of dichloromethane, 1.5 parts of organic silicone oil, 0.5 part of dimethylethanolamine, 0.5 part of stannous octoate, 15 parts of cellulose, 20 parts of super absorbent resin and 3 parts of deionized water. Wherein the super absorbent resin is polyacrylic acid super absorbent resin with the particle size of 200-410 mu m.
The preparation method of the hydrophilic soft sponge comprises the following steps:
s1, weighing the raw materials in parts by weight respectively.
S2, adding DEP-505S, universal polyether polyol, cellulose, super absorbent resin and deionized water into a storage vat, setting a constant material temperature at 20-23 ℃, and continuously stirring at a rotation speed of 120r/min for 10min to obtain a material A.
S3, uniformly mixing toluene diisocyanate, dimethylethanolamine, stannous octoate, organic silicone oil and dichloromethane, and preheating the material to 20-23 ℃ to obtain a material B.
And S4, conveying the material A and the material B to a high-speed mixer in proportion for high-speed stirring and mixing, and then conveying to an overflow groove for foaming to obtain the hydrophilic soft sponge.
The hydrophilic soft sponge of the present embodiment has a developed and interconnected pore structure and a polyurethane skeleton structure connecting the pore structures, and a super absorbent resin is bonded in the polyurethane skeleton structure.
Example 3
The hydrophilic soft sponge of the embodiment is prepared from the following raw materials in parts by weight: 27 parts of DEP-505S, 15 parts of universal polyether polyol, 20 parts of toluene diisocyanate, 10 parts of dichloromethane, 1.0 part of organic silicone oil, 0.8 part of dimethylethanolamine, 0.2 part of stannous octoate, 10 parts of cellulose, 10 parts of super absorbent resin and 2 parts of deionized water. Wherein the super absorbent resin is polyacrylic acid super absorbent resin with the particle size of 200-410 mu m.
The preparation method of the hydrophilic soft sponge comprises the following steps:
s1, weighing the raw materials in parts by weight respectively.
S2, adding DEP-505S, universal polyether polyol, cellulose, super absorbent resin and deionized water into a storage vat, setting a constant material temperature at 20-23 ℃, and continuously stirring at a rotation speed of 50r/min for 30min to obtain a material A.
S3, uniformly mixing toluene diisocyanate, dimethylethanolamine, stannous octoate, organic silicone oil and dichloromethane, and preheating the material to 20-23 ℃ to obtain a material B.
And S4, conveying the material A and the material B to a high-speed mixer in proportion for high-speed stirring and mixing, and then conveying to an overflow groove for foaming to obtain the hydrophilic soft sponge.
The hydrophilic soft sponge of the present embodiment has a developed and interconnected pore structure and a polyurethane skeleton structure connecting the pore structures, and a super absorbent resin is bonded in the polyurethane skeleton structure.
Example 4
The embodiment also comprises 0.5 part of surfactant, the nonionic surfactant is alkylphenol polyoxyethylene, and other components and parts by weight thereof are the same as those in embodiment 1.
The preparation method of the hydrophilic soft sponge comprises the following steps:
s1, weighing the raw materials in parts by weight respectively.
S2, adding DEP-505S, universal polyether polyol, cellulose, alkylphenol polyoxyethylene ether, super absorbent resin and deionized water into a storage vat, setting a constant material temperature of 20-23 ℃, and continuously stirring at a rotation speed of 15r/min for 60min to obtain a material A.
S3, uniformly mixing toluene diisocyanate, dimethylethanolamine, stannous octoate, organic silicone oil and dichloromethane, and preheating the material to 20-23 ℃ to obtain a material B.
And S4, conveying the material A and the material B to a high-speed mixer in proportion for high-speed stirring and mixing, and then conveying to an overflow groove for foaming to obtain the hydrophilic soft sponge.
Example 5
The embodiment also comprises 4.5 parts of a surfactant, the nonionic surfactant is polyoxyethylene lauryl ether, and other components and parts by weight of the nonionic surfactant are the same as those in the embodiment 2.
The preparation method of the hydrophilic soft sponge comprises the following steps:
s1, weighing the raw materials in parts by weight respectively.
S2, adding DEP-505S, universal polyether polyol, cellulose, polyoxyethylene lauryl ether, super absorbent resin and deionized water into a storage vat, setting a constant material temperature of 20-23 ℃, and continuously stirring at a rotation speed of 120r/min for 10min to obtain a material A.
S3, uniformly mixing toluene diisocyanate, dimethylethanolamine, stannous octoate, organic silicone oil and dichloromethane, and preheating the material to 20-23 ℃ to obtain a material B.
And S4, conveying the material A and the material B to a high-speed mixer in proportion for high-speed stirring and mixing, and then conveying to an overflow groove for foaming to obtain the hydrophilic soft sponge.
Example 6
The embodiment also comprises 2 parts of a surfactant, the nonionic surfactant is isomeric tridecanol ether, and other components and parts by weight of the components are the same as those in the embodiment 3.
The preparation method of the hydrophilic soft sponge comprises the following steps:
s1, weighing the raw materials in parts by weight respectively.
S2, putting DEP-505S, universal polyether polyol, cellulose, isomeric tridecanol ether, super absorbent resin and deionized water into a storage barrel, setting a constant material temperature of 20-23 ℃, and continuously stirring at a rotation speed of 50r/min for 30min to obtain a material A.
S3, uniformly mixing toluene diisocyanate, dimethylethanolamine, stannous octoate, organic silicone oil and dichloromethane, and preheating the material to 20-23 ℃ to obtain a material B.
And S4, conveying the material A and the material B to a high-speed mixer in proportion for high-speed stirring and mixing, and then conveying to an overflow groove for foaming to obtain the hydrophilic soft sponge.
Example 7
The embodiment also comprises 1 part of the silicon-phosphorus-aluminum zeolite molecular sieve which is subjected to acidizing and surface coupling coating, and other components and parts by weight are the same as those in the embodiment 1. The particle size of the silicon-phosphorus-aluminum zeolite molecular sieve is 0.5um, and the specific surface area is 750m2/g。
The process method for carrying out acidification and surface coupling coating treatment on the silicon-phosphorus-aluminum zeolite molecular sieve comprises the following steps: the silicoaluminophosphate zeolite molecular sieve is placed into a citric acid microcapsule solution to enable the concentration of the silicoaluminophosphate zeolite molecular sieve to be 5% -20%, then the silicon aluminophosphate zeolite molecular sieve is subjected to ultrasonic treatment for 4-6 hours, then is subjected to suction filtration, and is dried at the temperature of 40-45 ℃ to reach constant weight. Then, silane coupling agent (such as vinyl tri (beta-methoxyethoxy) silane and vinyl triethoxysilane) containing vinyl with the mass fraction of 0.5 percent relative to the silicoaluminophosphate zeolite molecular sieve is adopted to carry out coupling coating treatment on the surface of the silicoaluminophosphate zeolite molecular sieve.
The preparation method of the hydrophilic soft sponge comprises the following steps:
s1, weighing the raw materials in parts by weight respectively.
S2, putting DEP-505S, general polyether polyol, cellulose, a silicon-phosphorus-aluminum zeolite molecular sieve, super absorbent resin and deionized water into a storage vat, setting a constant material temperature of 20-23 ℃, and continuously stirring at a rotation speed of 15r/min for 60min to obtain a material A.
S3, uniformly mixing toluene diisocyanate, dimethylethanolamine, stannous octoate, organic silicone oil and dichloromethane, and preheating the material to 20-23 ℃ to obtain a material B.
And S4, conveying the material A and the material B to a high-speed mixer in proportion for high-speed stirring and mixing, and then conveying to an overflow groove for foaming to obtain the hydrophilic soft sponge.
Example 8
The embodiment also comprises 15 parts of silica powder subjected to acidification and surface coupling coating, and other components and parts by weight are the same as those in the embodiment 5. The granularity of the silica gel powder is 15um, and the specific surface area is 538m2/g。
The process method for acidifying and surface coupling coating treatment of silica gel powder comprises the following steps: putting the silica gel powder into the citric acid microcapsule solution to ensure that the concentration of the silica gel powder is 5-20%, then carrying out ultrasonic treatment for 4-6 hours, carrying out suction filtration, and drying at 40-45 ℃ to constant weight. Then, the surface of the silica gel powder is subjected to coupling coating treatment by adopting a silane coupling agent (such as gamma-aminopropyltriethoxysilane) containing amino in an amount of 0.5 percent by mass relative to the silica gel powder.
The preparation method of the hydrophilic soft sponge comprises the following steps:
s1, weighing the raw materials in parts by weight respectively.
S2, putting DEP-505S, universal polyether polyol, cellulose, silica gel powder, polyoxyethylene lauryl ether, super absorbent resin and deionized water into a storage barrel, setting the constant material temperature at 20-23 ℃, and continuously stirring at the rotating speed of 120r/min for 10min to obtain a material A.
S3, uniformly mixing toluene diisocyanate, dimethylethanolamine, stannous octoate, organic silicone oil and dichloromethane, and preheating the material to 20-23 ℃ to obtain a material B.
And S4, conveying the material A and the material B to a high-speed mixer in proportion for high-speed stirring and mixing, and then conveying to an overflow groove for foaming to obtain the hydrophilic soft sponge.
Example 9
The present example also includes 7 parts of montmorillonite powder subjected to acidification and surface coupling coating treatment, and the other components and the parts by weight thereof are the same as those in example 6. The particle size of the montmorillonite powder is 10um, and the specific surface area is 623m2/g。
The process method for carrying out acidification and surface coupling coating treatment on the montmorillonite powder comprises the following steps: the montmorillonite powder is put into a citric acid microcapsule solution to ensure that the concentration of the montmorillonite powder is 5-20 percent, and then the montmorillonite powder is subjected to ultrasonic treatment for 4-6 hours, then is subjected to suction filtration and is dried to constant weight at 40-45 ℃. Then, the surface of the porous adsorption powder is subjected to coupling coating treatment by adopting a silane coupling agent (such as beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane) containing an epoxy group, wherein the mass fraction of the silane coupling agent is 0.5 percent relative to the mass fraction of the montmorillonite powder.
The preparation method of the hydrophilic soft sponge comprises the following steps:
s1, weighing the raw materials in parts by weight respectively.
S2, putting DEP-505S, universal polyether polyol, cellulose, montmorillonite powder, isomeric tridecanol ether, super absorbent resin and deionized water into a storage barrel, setting the constant material temperature at 20-23 ℃, and continuously stirring at the rotation speed of 50r/min for 30min to obtain a material A.
S3, uniformly mixing toluene diisocyanate, dimethylethanolamine, stannous octoate, organic silicone oil and dichloromethane, and preheating the material to 20-23 ℃ to obtain a material B.
And S4, conveying the material A and the material B to a high-speed mixer in proportion for high-speed stirring and mixing, and then conveying to an overflow groove for foaming to obtain the hydrophilic soft sponge.
Comparative example 1
The sponge of the embodiment is prepared from the following raw materials in parts by weight: 20 parts of DEP-505S, 5 parts of dichloromethane, 0.5 part of organic silicone oil, 0.1 part of dimethylethanolamine, 0.1 part of stannous octoate, 1 part of super absorbent resin and 1.5 parts of deionized water. Wherein the super absorbent resin is polyacrylic acid super absorbent resin with the particle size of 200-410 mu m. A sponge was prepared by the procedure of example 1.
Comparative example 2
The sponge of the embodiment is prepared from the following raw materials in parts by weight: 20 parts of universal polyether polyol, 5 parts of dichloromethane, 0.5 part of organic silicone oil, 0.1 part of dimethylethanolamine, 0.1 part of stannous octoate, 1 part of super absorbent resin and 1.5 parts of deionized water. Wherein the super absorbent resin is polyacrylic acid super absorbent resin with the particle size of 200-410 mu m. A sponge was prepared by the procedure of example 1.
Absorption Performance test
1. Sample (I)
Test samples: examples 1 to 9, test samples were cut out into long strips in the dimensions of 400mm in length, 10mm in width and 5mm in thickness.
Comparative sample: comparative example 1-comparative example 2 the sponge was prepared by cutting a comparative sample into long strips having a size length of 400mm, a width of 10mm and a thickness of 5mm, respectively.
Diaper test sample or diaper comparative sample: the composite absorption core body in the paper diaper is replaced by the test sample or the comparison sample through a manual process, and the steps are as follows:
step 1, taking out the paper diaper from a commercially available L-shaped paper diaper commodity, stretching the paper diaper in the longitudinal and transverse directions to be in a completely unfolded state, and fixing the paper diaper on a sample fixing plate with a magic hook tape on the surface layer in an upward mode.
And 2, separating the liquid-permeable surface layer, the leakage-proof partition edge and the liquid-impermeable bottom layer of the paper diaper from the composite absorption core body respectively in a hair dryer heating mode, and taking out the composite absorption core body.
And 3, spraying glue on one or two surfaces of the test sample or the comparison sample by a glue machine, wherein the glue type is selected from large spiral glue spraying.
And 4, placing the test sample or the comparison sample subjected to glue spraying treatment on the surface layer between the liquid-permeable surface layer and the liquid-impermeable bottom layer, pressing and fixing, and spraying glue on the leakage-proof separation edge for fixing to obtain the paper diaper test sample.
2. Test method
Test liquid: adding blue pigment in normal saline.
And secondly, the rewet amount of a paper diaper test sample and a paper diaper comparison sample is determined by referring to the test steps for rewet amount determination in the paper diaper (sheet and pad) standard GB/T28004 and 2011.
Timing is started from the moment the liquid contacts the sample surface until the liquid completely disappears from the surface of the sample as the absorption rate.
Fourthly, testing the diffusion length: after the rewet level is tested, the maximum diffusion length of the liquid along the longitudinal direction of the sample is measured using a ruler.
Flexibility: qualitative comparison is adopted, and an evaluation group consisting of 10 persons is selected to visually compare the softness of the sample through touch and hand feeling respectively.
3. Results of absorption Performance test
The test results are shown in the following table:
TABLE 1 absorbency of hydrophilic soft sponge absorbent cores
Figure BDA0002695279510000111
As can be seen from the data of the performance test results in Table 1, the hydrophilic soft sponges prepared in examples 1-9 of the present invention have excellent softness, increased water absorption capacity and diffusion length with the increase of the amount of the super absorbent resin, increased water absorption rate, and greatly decreased rewet with the increase of the amount of the super absorbent resin.
The data in the table show that the polyether polyol with high EO content, the general polyether polyol and the cellulose are compounded, the polyether polyol with high EO content, which has higher hydrophilic performance and softness performance, can be generated on the product, the hydrophilicity is further improved, and the cellulose with a large number of hydroxyl groups is matched, so that the polyether polyol has higher hydrophilic activity, the hydrophilicity of the hydrophilic soft sponge is improved, and the water absorption rate of the hydrophilic soft sponge is improved.
The data in the table show that the sponge formed by polymerizing the polyether polyol with the high EO content has super-soft hand feeling, and the collapse phenomenon is easy to generate when the sponge is used as an absorption core due to the super-soft, so that the super absorbent resin combined in the sponge has serious quality problems of serious reduction of absorption capacity and water absorption rate due to the lack of a diversion channel, and serious rewet increase, even the side leakage situation, and the use requirement of the disposable sanitary product is difficult to meet. However, the sponge made of pure general-purpose polyether polyol is hard, which also affects the quality of the disposable sanitary product and the wearing experience of consumers, and reduces the comfort. The invention can produce good indentation hardness to obtain common general polyether polyol with good resilience and polyether polyol with high EO content to compound, and give full play to the synergistic effect of the two, on one hand, the sponge has certain hydrophilic performance, the hydrophilic performance and the softness are improved, on the other hand, the sponge has better resilience, and the obtained hydrophilic soft sponge has excellent hydrophilicity, softness and resilience, thereby endowing the hydrophilic soft sponge with the characteristics of high water absorption rate, high water absorption speed, high water retention, excellent liquid diffusion and passing performance, high water absorption capacity, difficult dehydration and good water retention when being acted by external force.
The flexibility of this example was: super-soft > softer > harder.
Testing the odor removal performance: the urea in the urine is decomposed into ammonium hydroxide under the action of bacterial urolytic enzyme, so that the pH value of the urine is increased, and when the pH value is more than 7.0, free ammonia is easily released. Thus, the hydrophilic soft sponges prepared in examples 6-9 were subjected to ammonia absorption and deodorization tests, the results of which are shown in Table 2, and the specific test methods were as follows:
the multi-hydrophilic soft sponges of examples 6-9 were cut into test specimens having a size of 10cm by 50 cm.
Six 51PVF resin air bags were prepared, and one sample specimen was put into each of five air bags, and the other air bag was used as a blank test. Then, 500ppm NH were blown into six air bags3And sealing. Measuring NH in the balloon after 2 hours using a gas detection tube3The concentration of (c). The test results were as follows:
TABLE 2 results of the Performance testing of various samples
Figure BDA0002695279510000121
As can be seen from the data of the performance test results in Table 2, the porous adsorption powder after the acidification pretreatment is added into the raw material formula for preparing the hydrophilic sponge, so that the hydrophilic sponge can adsorb and neutralize alkaline substances, such as ammonia. Therefore, the hydrophilic soft sponges prepared in examples 7-9 of the present invention had excellent deodorizing effects.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner; as will be readily apparent to those skilled in the art from the disclosure herein, the present invention may be practiced without these specific details; however, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention; meanwhile, any changes, modifications, and evolutions of the equivalent changes of the above embodiments according to the actual techniques of the present invention are still within the protection scope of the technical solution of the present invention.

Claims (5)

1. Taste-inhibiting hydrophilic soft sponge based on silicoaluminophosphate zeolite molecular sieve is characterized in that: the feed is prepared from the following raw materials in parts by weight: 10.9 parts of DEP-505S, 9.1 parts of universal polyether polyol, 10 parts of toluene diisocyanate, 5 parts of dichloromethane, 0.5 part of organic silicone oil, 0.1 part of dimethylethanolamine, 0.1 part of stannous octoate, 5 parts of cellulose, 1 part of super absorbent resin and 1.5 parts of deionized water; 1 part of silicon-phosphorus-aluminum zeolite molecular sieve subjected to acidification and surface coupling coating treatment, wherein the particle size of the silicon-phosphorus-aluminum zeolite molecular sieve is 0.5um, and the specific surface area is 750m2/g；
The process method for carrying out acidification and surface coupling coating treatment on the silicon-phosphorus-aluminum zeolite molecular sieve comprises the following steps:
the method comprises the steps of putting a silicon-phosphorus-aluminum zeolite molecular sieve into a citric acid microcapsule solution to enable the concentration of the silicon-phosphorus-aluminum zeolite molecular sieve to be 5% -20%, performing ultrasonic treatment for 4-6 hours, performing suction filtration, drying at 40-45 ℃ to constant weight, and performing coupling coating treatment on the surface of the silicon-phosphorus-aluminum zeolite molecular sieve by using a vinyl-containing silane coupling agent with the mass fraction of 0.5% relative to the silicon-phosphorus-aluminum zeolite molecular sieve.
2. The odor-suppressing hydrophilic soft sponge based on a silicoaluminophosphate zeolite molecular sieve of claim 1, wherein: the DEP-505S has a functionality of 3 and a molecular weight of 3300.
3. The odor-suppressing hydrophilic soft sponge based on a silicoaluminophosphate zeolite molecular sieve of claim 1, wherein: the deodorization rate of the hydrophilic soft sponge to ammonia gas is 62%.
4. The odor-suppressing hydrophilic soft sponge based on a silicoaluminophosphate zeolite molecular sieve of claim 1, wherein: the silane coupling agent is vinyl tri (beta-methoxyethoxy) silane or vinyl triethoxysilane.
5. A process for the preparation of an odour-inhibiting hydrophilic soft sponge based on a silicoaluminophosphate zeolite molecular sieve as claimed in any one of claims 1 to 4, comprising the steps of:
s1, weighing the raw materials in parts by weight respectively;
s2, putting DEP-505S, general polyether polyol, cellulose, a silicon-phosphorus-aluminum zeolite molecular sieve, super absorbent resin and deionized water into a storage bucket, setting a constant material temperature of 20-23 ℃, and continuously stirring at a rotation speed of 15r/min for 60min to obtain a material A;
s3, uniformly mixing toluene diisocyanate, dimethylethanolamine, stannous octoate, organic silicone oil and dichloromethane, and preheating the material to 20-23 ℃ to obtain a material B;
s4, conveying the material A and the material B to a high-speed mixer in proportion for high-speed stirring and mixing, and then conveying to an overflow groove for foaming to prepare the odor-inhibiting hydrophilic soft sponge based on the silicoaluminophosphate zeolite molecular sieve.
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