CN114891340A - Fragrant shape memory composite foam material and preparation method thereof - Google Patents
Fragrant shape memory composite foam material and preparation method thereof Download PDFInfo
- Publication number
- CN114891340A CN114891340A CN202210634599.9A CN202210634599A CN114891340A CN 114891340 A CN114891340 A CN 114891340A CN 202210634599 A CN202210634599 A CN 202210634599A CN 114891340 A CN114891340 A CN 114891340A
- Authority
- CN
- China
- Prior art keywords
- essential oil
- shape memory
- fragrance
- memory composite
- polyurethane
- 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.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 239000006261 foam material Substances 0.000 title claims description 19
- 238000002360 preparation method Methods 0.000 title claims description 11
- 239000000341 volatile oil Substances 0.000 claims abstract description 72
- 239000000463 material Substances 0.000 claims abstract description 63
- 238000005187 foaming Methods 0.000 claims abstract description 34
- 239000003094 microcapsule Substances 0.000 claims abstract description 32
- 229920002635 polyurethane Polymers 0.000 claims abstract description 27
- 239000004814 polyurethane Substances 0.000 claims abstract description 27
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 24
- 239000004005 microsphere Substances 0.000 claims abstract description 22
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 20
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 20
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 20
- 238000001179 sorption measurement Methods 0.000 claims abstract description 18
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 238000011049 filling Methods 0.000 claims abstract description 9
- 239000002585 base Substances 0.000 claims abstract description 5
- 238000001338 self-assembly Methods 0.000 claims abstract description 5
- 239000002121 nanofiber Substances 0.000 claims abstract description 4
- 239000003205 fragrance Substances 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000011863 silicon-based powder Substances 0.000 claims description 11
- 239000000839 emulsion Substances 0.000 claims description 10
- 230000001376 precipitating effect Effects 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000011858 nanopowder Substances 0.000 claims description 9
- 239000012744 reinforcing agent Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000011162 core material Substances 0.000 claims description 6
- 239000011258 core-shell material Substances 0.000 claims description 6
- 239000003995 emulsifying agent Substances 0.000 claims description 6
- 238000013268 sustained release Methods 0.000 claims description 5
- 239000012730 sustained-release form Substances 0.000 claims description 5
- 235000009024 Ceanothus sanguineus Nutrition 0.000 claims description 4
- 244000178870 Lavandula angustifolia Species 0.000 claims description 4
- 235000010663 Lavandula angustifolia Nutrition 0.000 claims description 4
- 240000003553 Leptospermum scoparium Species 0.000 claims description 4
- 235000015459 Lycium barbarum Nutrition 0.000 claims description 4
- 241000220317 Rosa Species 0.000 claims description 4
- 239000001102 lavandula vera Substances 0.000 claims description 4
- 235000018219 lavender Nutrition 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 241000196324 Embryophyta Species 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- RMGVATURDVPNOZ-UHFFFAOYSA-M potassium;hexadecyl hydrogen phosphate Chemical compound [K+].CCCCCCCCCCCCCCCCOP(O)([O-])=O RMGVATURDVPNOZ-UHFFFAOYSA-M 0.000 claims description 3
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 3
- 238000000265 homogenisation Methods 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 abstract description 5
- 230000006870 function Effects 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000002775 capsule Substances 0.000 abstract 2
- 239000004088 foaming agent Substances 0.000 abstract 1
- 230000007774 longterm Effects 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 21
- 239000010410 layer Substances 0.000 description 15
- 229920005830 Polyurethane Foam Polymers 0.000 description 14
- 239000011496 polyurethane foam Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 229910021642 ultra pure water Inorganic materials 0.000 description 6
- 239000012498 ultrapure water Substances 0.000 description 6
- 239000006260 foam Substances 0.000 description 5
- 239000012258 stirred mixture Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 230000001976 improved effect Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 235000003261 Artemisia vulgaris Nutrition 0.000 description 3
- 240000006891 Artemisia vulgaris Species 0.000 description 3
- 229920000079 Memory foam Polymers 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 239000008210 memory foam Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 239000012792 core layer Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000431 shape-memory polymer Polymers 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000000707 layer-by-layer assembly Methods 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0085—Use of fibrous compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a fragrant shape memory composite foaming material, which takes nanofiber reinforced shape memory polyurethane as a base material, aromatic-containing microspheres as a composite filling material, silicon and alkali as foaming agents, the aromatic-containing microspheres as essential oil microcapsules prepared by adopting an electrostatic adsorption layer-by-layer nano self-assembly technology, essential oil as a capsule core, and polyethyleneimine and sodium carboxymethylcellulose as a capsule wall. The invention not only can enhance the strength and rigidity of the foaming material, but also endows the foaming material with a long-term, stable and slow-release fragrance-retaining function.
Description
Technical Field
The field belongs to the technical field of packaging material processing, and particularly relates to a shape memory composite foaming material with fragrance and a preparation method thereof.
Background
The shape memory polymer is a polymer foaming material which can deform and keep a temporary shape under a certain external force, and then gradually recover to the original shape from the temporary shape, and the change process is reversible for many times. The material has the advantages of low cost, low density, high shape recovery, easy processing and the like, and has wide application in the fields of aerospace, biomedicine, power electronics, packaging, intelligent control systems and the like.
The polyurethane-based shape memory foam material as a newly developed shape memory polymer material has a three-dimensional porous structure, generally consists of a stationary phase and a softening-hardening reversible phase, has shape memory characteristics through driving and inducing reversible change of the reversible phase, and has the advantages of wide recovery temperature range, easy adjustment of structural components, good biocompatibility and the like. However, the pure shape memory polyurethane material has poor mechanical properties such as rigidity and strength, poor shape memory and single property, so the application occasion is limited. The polymer-based composite material can be prepared by filling the reinforcing material and adding raw materials with special functions, so that the composite material has multiple functions, the mechanical strength and the toughness are greatly improved, and the market competitiveness is improved.
For example, tea tree essential oil can be added in the forming and processing process of the foaming material, so that peculiar smell inherent in the foaming material or generated in the processing process can be covered, the fragrance emission requirement of a product can be met, and the additional function of the foaming material is added. However, the processing of the foaming material needs a high temperature of more than 100 ℃, most of the perfume is volatilized, and meanwhile, a plurality of additives such as a plasticizer, a stabilizer, a filler, a pigment and the like are mixed in the injection molding or granulation processing of a plurality of foaming materials, and the additives may have chemical reactions with various perfumes in the tea tree essential oil to influence the performances such as the fragrance, the color and the mechanical properties of the foaming materials and the like.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a shape memory composite foaming material with fragrance and a preparation method thereof.
In order to achieve the above object, the present invention adopts the following technical solutions:
the shape memory composite foam material with fragrance comprises a foam material and a filling material, wherein the foam material takes nano-fiber reinforced polyurethane as a base material, the filling material is a fragrance-containing microsphere, the fragrance-containing microsphere is an essential oil slow-release microcapsule with a multilayer core-shell structure, the essential oil slow-release microcapsule comprises a core material and a wall material, the core material is essential oil, and the wall material is prepared by carrying out nano self-assembly on polyethyleneimine and sodium carboxymethylcellulose layer by layer through electrostatic adsorption.
A preparation method of a shape memory composite foaming material with fragrance comprises the following specific steps:
(1) blending polyurethane and a reinforcing agent according to a certain mass ratio, uniformly stirring, and adding a proper amount of silicon powder;
(2) adding the fragrant microspheres according to a proportion, fully stirring, adding a curing agent, and reacting for a period of time;
(3) adding alkali liquor, fully stirring, pouring the mixture into a mould, foaming, curing and forming, and then demoulding to obtain the fragrant shape memory composite foaming material.
Preferably, in the step (1), the reinforcing agent is carbon nano powder or chopped carbon fiber; the mass ratio of the polyurethane to the reinforcing agent is (8-15): 1, silicon powder accounts for 3-15% of the mass of the polyurethane.
Preferably, in the step (2), the curing agent is one of A33, ALT-101 or ALT-401; the curing agent accounts for 0.2-2% of the mass of the polyurethane, and the fragrant microspheres account for 5-20% of the mass of the polyurethane.
Preferably, in the step (3), the alkali solution is a NaOH aqueous solution or a KOH aqueous solution, and the mass fraction of the alkali solution is 30-50%; the molar ratio of alkali to silicon powder is 2: 1; the foaming and curing time is 12-24 h, and the temperature is room temperature.
Preferably, in the step (2), the preparation of the aroma-containing microspheres comprises the following steps:
s1, adding the essential oil and the emulsifier into a beaker filled with deionized water, uniformly mixing, and carrying out high-pressure homogenization treatment for a plurality of times to obtain an essential oil emulsion;
s2, sucking a proper amount of essential oil emulsion into a centrifuge tube, adding a polyethyleneimine water solution, mixing, stirring, adsorbing for a period of time, and centrifuging, washing and precipitating;
s3, adding sodium carboxymethylcellulose aqueous solution, mixing, stirring, adsorbing for a period of time, and centrifuging, washing and precipitating;
s4, repeating the adsorption and washing steps to obtain the essential oil slow-release microcapsule with a multilayer core-shell structure, namely the fragrant microspheres.
Preferably, in step S1, the essential oil is natural plant essential oil selected from one of folium artemisiae argyi essential oil, lavender essential oil, tea tree essential oil or rose essential oil; the emulsifier is anionic surfactant selected from one or more of sodium stearate, potassium cetyl phosphate or sodium dodecyl sulfate; the concentration of the essential oil in the deionized water is 5-15%, and the emulsifier accounts for 5-10% of the mass of the essential oil; the high-pressure homogenizing pressure is 600-1200 bar, and the cycle time is 5-20 times.
Preferably, in step S2, the concentration of the polyethyleneimine aqueous solution is 3 to 10mg/mL, and the mass ratio of the polyethyleneimine to the essential oil is (0.1 to 0.3): 1; the adsorption time is 5-10 min, the centrifugal rotating speed is 3000-6000 r/min, the centrifugal time is 10-40 min, and the washing times are 3-5.
Preferably, in step S3, the concentration of the sodium carboxymethyl cellulose aqueous solution is 1 to 5mg/mL, and the mass ratio of the sodium carboxymethyl cellulose to the polyethyleneimine is (0.5 to 2): 1; the adsorption time is 5-10 min, the centrifugal rotating speed is 3000-6000 r/min, the centrifugal time is 10-40 min, and the washing times are 3-5.
Preferably, in the step S4, the total number of layers of the essential oil sustained-release microcapsules is one of 2 to 10.
The invention has the advantages that:
(1) according to the invention, an electrostatic adsorption layer-by-layer nano self-assembly technology is adopted, and polyethyleneimine and sodium carboxymethylcellulose shells with opposite charges are deposited on a core layer by layer to obtain the target microcapsule with a multilayer core-shell structure, wherein plant essential oil is emulsified by an anionic surfactant and then has negative charges on the surface, and polyethyleneimine and sodium carboxymethylcellulose solutions respectively have positive charges and negative charges, so that the multilayer microcapsule shells can be formed on the surface of an essential oil core material through electrostatic adsorption, and the microcapsule has better mechanical properties;
(2) the shape memory composite foam material prepared by the invention takes the polyurethane reinforced by the nano-fiber as the base material and takes the fragrance-containing microspheres as the filling material, thereby not only improving the mechanical strength and toughness of the shape memory foam material, but also endowing the shape memory composite foam material with a slow-release fragrance-containing function; the shell of the aromatic microsphere contains solidified polyethyleneimine, and the aromatic microsphere has certain compatibility with the base material polyurethane of the foam material, so that the aromatic microsphere can be uniformly dispersed into the shape memory foam material mother liquor, and is favorable for mixing and processing molding.
Drawings
FIG. 1 is a diagram of a compressed sample of example 1: (a) before compression, (b) after compression, (c) after recovery;
FIG. 2 is a cross-sectional profile of a polarizing electron microscope of a sample: (a) example 1, (b) comparative example 2;
FIG. 3 is a graph showing the retention of fragrance of the samples of example 1 and comparative example 3 with time.
Detailed Description
The invention is described in detail below with reference to the figures and the embodiments.
Example 1
A preparation method of a shape memory composite foaming material with fragrance comprises the following specific steps:
(1) 50g of molten polyurethane and 6.25g of carbon nano powder are blended, stirred uniformly and added with 4g of silicon powder;
(2) adding 5g of folium Artemisiae Argyi essential oil and 0.5g of sodium dodecyl sulfate into a beaker containing deionized water to 50mL, mixing well, and homogenizing under high pressure at 1000bar for 10 times to obtain essential oil emulsion; precisely sucking a proper amount of emulsion into a 5mL centrifuge tube, adding 170mL of polyethyleneimine water solution with the concentration of 3mg/mL, mixing, stirring and adsorbing for 10min, and then centrifugally washing and precipitating for 4 times with ultra-pure water at 3000r/min, wherein each time is 10 min; then adding 100mL of sodium carboxymethylcellulose aqueous solution with the concentration of 2.5mg/mL, mixing, stirring and adsorbing for 10min, and then centrifugally washing and precipitating for 4 times with ultrapure water at 3000r/min, wherein each time lasts for 10 min; repeating the steps of adsorption (polyethyleneimine/sodium carboxymethylcellulose) and washing for 2 times to obtain the double-layer essential oil sustained-release microcapsule with 4 layers.
(3) Adding 6g of the fragrant microspheres in the step (1), fully stirring, then adding 0.25g of curing agent A33, and fully and uniformly stirring;
(4) adding 28g of prepared NaOH aqueous solution with the mass fraction of 30%, pouring the stirred mixture into a mold, foaming and curing at room temperature for 12h, and demolding after molding to prepare the shape memory composite polyurethane foam material containing the mugwort fragrance.
Example 2
A preparation method of a shape memory composite foaming material with fragrance comprises the following specific steps:
(1) blending 50g of molten polyurethane and 5g of chopped carbon fibers, uniformly stirring, and adding 2.8g of silicon powder;
(2) adding 5g of lavender essential oil and 0.4g of sodium stearate into a beaker filled with deionized water to 50mL, uniformly mixing, and homogenizing under high pressure of 1100bar for 8 times to obtain an essential oil emulsion; precisely sucking a proper amount of emulsion into a 5mL centrifuge tube, adding 125mL of polyethyleneimine water solution with the concentration of 8mg/mL, mixing, stirring and adsorbing for 8min, and centrifugally washing and precipitating for 4 times with ultrapure water at 5000r/min, wherein each time is 10 min; then adding 100mL of sodium carboxymethylcellulose aqueous solution with the concentration of 5mg/mL, mixing, stirring and adsorbing for 10min, and centrifugally washing and precipitating for 4 times with ultrapure water at 3000r/min, wherein each time lasts for 10-4 min; repeating the steps of adsorption (polyethyleneimine/sodium carboxymethylcellulose) and washing for 4 times to obtain the double-layer essential oil sustained-release microcapsule with 8 layers.
(3) Adding 2.5g of fragrant microspheres into the step (1), fully stirring, then adding 0.4g of curing agent ALT-101, and fully and uniformly stirring;
(4) adding 20g of prepared 40% NaOH aqueous solution, pouring the stirred mixture into a mold, foaming and curing at room temperature for 12h, and demolding after molding to obtain the shape memory composite polyurethane foam material containing lavender fragrance.
Example 3
A preparation method of a shape memory composite foaming material with fragrance comprises the following specific steps:
(1) 50g of molten polyurethane and 4.55g of carbon nano powder are blended, stirred uniformly and added with 6g of silicon powder;
(2) adding 5g of rose essential oil and 0.35g of potassium cetyl phosphate into a beaker containing deionized water until the volume is 50mL, uniformly mixing, and homogenizing for 8 times at high pressure of 1200bar to obtain essential oil emulsion; precisely sucking a proper amount of emulsion into a 5mL centrifuge tube, adding 150mL of polyethyleneimine water solution with the concentration of 10mg/mL, mixing, stirring and adsorbing for 10min, and then centrifugally washing and precipitating for 4 times with ultrapure water at 5000r/min, wherein each time is 10 min; then adding 120mL of sodium carboxymethylcellulose aqueous solution with the concentration of 5mg/mL, mixing, stirring and adsorbing for 10min, and then centrifugally washing and precipitating for 4 times with ultrapure water at 3000r/min, wherein each time lasts for 10-4 min; repeating the steps of adsorption (polyethyleneimine/sodium carboxymethylcellulose) and washing for 2 times to obtain the double-layer essential oil sustained-release microcapsule with 4 layers.
(3) Adding 9g of the fragrant microspheres in the step (1), fully stirring, then adding 0.47g of curing agent A33, and fully and uniformly stirring;
(4) adding 43g of prepared KOH aqueous solution with the mass fraction of 40%, pouring the stirred mixture into a mold, foaming and curing at room temperature for 12h, and demolding after molding to prepare the shape memory composite polyurethane foam material with the rose fragrance.
Comparative example 1
The comparative example differs from example 1 in that: no reinforcing agent is added to the foamed material.
Comparative example 2
The comparative example differs from example 1 in that: the foaming material is not added with the fragrant microspheres, and comprises the following specific steps:
(1) 50g of molten polyurethane and 6.25g of carbon nano powder are blended, stirred uniformly and added with 4g of silicon powder;
(2) after fully stirring, adding 0.25g of curing agent A33, and fully stirring uniformly;
(3) adding 28g of prepared 40% NaOH aqueous solution, pouring the stirred mixture into a mold, foaming and curing at room temperature for 12h, and demolding after molding to prepare the shape memory composite polyurethane foam material.
Comparative example 3
The comparative example differs from example 1 in that: the essential oil is not microencapsulated and comprises the following specific steps:
(1) 50g of molten polyurethane and 6.25g of carbon nano powder are blended, stirred uniformly and added with 4g of silicon powder;
(2) adding 2.5g of mugwort essential oil into the step (1), fully stirring, adding 0.25g of curing agent A33, and fully and uniformly stirring;
(3) adding 28g of prepared 40% NaOH aqueous solution, pouring the stirred mixture into a mold, foaming and curing at room temperature for 12h, and demolding after molding to obtain the shape memory composite polyurethane foam material containing the mugwort fragrance.
Comparative example 4
The comparative example differs from example 1 in that: in the process of microencapsulation, only polyethyleneimine solution is used for adsorption, and the total times are 4 times (namely, the adsorption of the two sodium carboxymethyl cellulose aqueous solutions is replaced by the polyethyleneimine solution).
Test analysis
1. Microencapsulation efficiency test
(1) The test method comprises the following steps: preparing essential oil standard sample with certain concentration gradient by using absolute ethyl alcohol as solvent, and performing ultraviolet spectrophotometryAnd scanning the samples in sequence, respectively measuring the absorbance of the samples under the maximum absorption wavelength, and calculating a linear regression equation for drawing the concentration to the absorbance. Adding absolute ethanol into the solution filtered from the microcapsule reaction stock solution to 500mL, taking 10mL to test the light absorption intensity Y of the solution at the maximum absorption wavelength, calculating the concentration C and the mass M of the essential oil in the filtrate according to the light absorption intensity, and adding the total mass of the essential oil in the experiment to be M 0 . The envelope rate δ is calculated as:
δ＝100％×(M 0 -M)/M 0
(2) test results
The microcapsules prepared in examples 1-3 were tested for encapsulation efficiency, and the results are shown in table 1:
table 1 microencapsulation efficiency test
| Serial number | Encapsulation efficiency/% |
| Example 1 | 98.25 |
| Example 2 | 95.09 |
| Example 3 | 96.33 |
It can be seen from table 1 that by using the electrostatic adsorption layer-by-layer nano self-assembly technique, the polyethyleneimine and the sodium carboxymethylcellulose shells with opposite charges are deposited on the core layer by layer, and the obtained target microcapsule with a multilayer core-shell structure has excellent encapsulation efficiency which is over 95%.
2. Mechanical property of composite polyurethane foam material
The tensile properties, impact properties, and the like of the composite foamed materials prepared in examples 1, 1 and 2 were investigated using a general polyurethane foamed material without a reinforcing agent and microcapsules as a blank sample, and the test results are shown in table 2.
TABLE 2 mechanical Properties of the composite foams
| Serial number | Tensile strength/MPa | Tensile modulus/MPa | Impact Strength/(kJ/m) 2 ) |
| Blank sample | 15.2 | 214 | 3.1 |
| Example 1 | 21.7 | 521 | 3.8 |
| Comparative example 1 | 18.5 | 347 | 3.4 |
| Comparative example 2 | 20.3 | 388 | 3.6 |
As can be seen from Table 2, the addition of filler has a very significant effect on the tensile and impact properties of the syntactic foam. After the microcapsules were added in comparative example 1, the tensile strength and tensile modulus of the syntactic foam were increased by 21.7% and 62.1%, respectively, compared to the pure polyurethane foam blank. In comparative example 2, the tensile property and the impact property are greatly improved after only the reinforcing agent carbon nano powder is added, wherein the impact strength reaches 3.6kJ/m 2 . This shows that the two fillers have good bonding force with polyurethane, and have good dispersibility, and fully play a role in reinforcement.
In example 1, the tensile strength of the composite foam material prepared by filling the carbon nano powder and the microcapsule can reach 21.7MPa, and the tensile modulus can reach 521MPa, which are respectively increased by 42.8% and 143.4% compared with the pure polyurethane blank foam material, which indicates that the microcapsule and the carbon nano powder have a reinforcing effect on the polyurethane material, and when the material is subjected to a stress load, the material can be used as a stress bearing receptor to reinforce the stress bearing capacity and the impact resistance of the material because the filler and the polyurethane have good bonding force.
The syntactic foam prepared in example 1 was cut into short cylinders of 36mm diameter and 21mm height and subjected to a material memory cycling test, and the compressed samples are shown in FIG. 1. As can be seen from FIG. 1, the compressibility of the sample reaches 77%, and the recovery after relaxation is nearly 97%, which shows that the composite foam material prepared by the experiment has excellent shape memory capability.
3. Topography testing
The surface morphology of each of example 1 and comparative example 2 was observed with a polarizing electron microscope, and the difference in surface between the polyurethane foam material before and after filling was analyzed, and the results are shown in fig. 2.
As can be seen from the test results of the mechanical properties of the composite polyurethane foam material in Table 1, the addition of the microcapsules has no significant adverse effect on the tensile strength and the impact strength of the foam material. As can be seen from the sectional microscope photograph shown in fig. 2(a), since the microcapsules are several micrometers in size and relatively uniform, they are uniformly distributed without significantly affecting the mechanical properties of the foam itself.
4. Loss of essential oils during processing
The cost can be saved by reducing the volatilization of the essential oil in the processing process, the quality of the microcapsules prepared in the embodiments 1 to 3 and the comparative example 3 and the loss amount of the essential oil in the processing process are respectively weighed, and the specific results are shown in table 3.
TABLE 3 loss testing of essential oils
| Serial number | The addition amount of the original microcapsule per gram | Crude essential oil amount/g | Number of microcapsule layers | Loss of essential oil/g | The loss rate of essential oil is% |
| Comparative example 3 | 0 | 0 | 0 | 0.56 | 46.43 |
| Comparative example 4 | 6 | 1.2 | ---- | 0.37 | 31.22 |
| Example 1 | 6 | 1.2 | 4 | 0.06 | 5.16 |
| Example 2 | 6 | 1.2 | 8 | 0.04 | 3.53 |
| Example 3 | 9 | 1.8 | 4 | 0.09 | 7.69 |
It can be seen from table 3 that, in comparative example 3 in which essential oil is directly added, the loss rate is close to 50%, compared with the above, the effect after adding microcapsules is better, the loss of essential oil under the high-temperature processing condition can be controlled below 10%, the content of essential oil is increased with the increase of the addition amount of microcapsules, the volatilization is accelerated, the loss is also increased, and the loss rate of essential oil is reduced with the increase of the number of layers of the microcapsule shells, which indicates that the microcapsule strength can be improved by the multilayer shell coating, and the protection of inner core essential oil is increased. As can be seen from comparison of comparative example 4 and example 1, if only polyethyleneimine is adsorbed alone, although the total adsorption times is 4 times, the step of electrostatic self-assembly of sodium carboxymethyl cellulose is lacked, so that a good stable coating layer cannot be realized, and the loss of essential oil is still high.
5. Fragrance retention rate of composite polyurethane foam material
The aroma retention rates of the syntactic polyurethane foams prepared in example 1 and comparative example 3 were measured, the aroma retention period was evaluated by measuring the change in mass of the syntactic polyurethane foam with time by means of a precision balance, and it was found that the mass decreased was m and the total mass of the syntactic polyurethane foam added with essential oil was m 0 . The aroma retention rate R is calculated by the following formula:
R＝100％×(m 0 -m)/m 0
the detection result is shown in figure 3, and as can be seen from figure 3, the volatilization of the essential oil is fastest in the early stage, and gradually slows down with the lapse of time, and becomes gentle after 10 days. After the microencapsulated essential oil is filled into the foam material in the example 1, the volatilization speed of the essential oil is obviously slower than that of the microencapsulated essential oil, and after 12 months, the composite polyurethane foam material still has fragrance, which shows that the perfuming effect of the microcapsule has longer fragrance retention period.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It should be understood by those skilled in the art that the above embodiments do not limit the present invention in any way, and all technical solutions obtained by using equivalent alternatives or equivalent variations fall within the scope of the present invention.
Claims (10)
1. The shape memory composite foam material with fragrance is characterized by comprising a foam material and a filling material, wherein the foam material takes nanofiber reinforced polyurethane as a base material, the filling material is a fragrance-containing microsphere, the fragrance-containing microsphere is an essential oil slow-release microcapsule with a multilayer core-shell structure, the essential oil slow-release microcapsule comprises a core material and a wall material, the core material is essential oil, and the wall material is prepared by performing layer-by-layer nano self-assembly on polyethyleneimine and sodium carboxymethylcellulose through electrostatic adsorption.
2. The preparation method of the shape memory composite foaming material with fragrance as claimed in claim 1, characterized by comprising the following specific steps:
(1) blending polyurethane and a reinforcing agent according to a certain mass ratio, uniformly stirring, and adding a proper amount of silicon powder;
(2) adding the fragrant microspheres according to a proportion, fully stirring, adding a curing agent, and reacting for a period of time;
(3) adding alkali liquor, fully stirring, pouring the mixture into a mould, foaming, curing and forming, and then demoulding to obtain the fragrant shape memory composite foaming material.
3. The method for preparing the shape memory composite foam material with fragrance according to claim 2, wherein in the step (1), the reinforcing agent is carbon nano powder or chopped carbon fiber; the mass ratio of the polyurethane to the reinforcing agent is (8-15): 1, silicon powder accounts for 3-15% of the mass of the polyurethane.
4. The method for preparing the scented shape memory composite foam material according to claim 2, wherein in the step (2), the curing agent is one of A33, ALT-101 or ALT-401; the curing agent accounts for 0.2-2% of the mass of the polyurethane, and the fragrant microspheres account for 5-20% of the mass of the polyurethane.
5. The method for preparing the shape memory composite foam material with fragrance according to claim 2, wherein in the step (3), the alkali solution is NaOH aqueous solution or KOH aqueous solution, and the mass fraction of the alkali solution is 30-50%; the molar ratio of alkali to silicon powder is 2: 1; the foaming and curing time is 12-24 h, and the temperature is room temperature.
6. The method for preparing the shape memory composite foaming material with fragrance according to claim 2, wherein in the step (2), the preparation steps of the fragrance-containing microspheres are as follows:
s1, adding the essential oil and the emulsifier into a beaker filled with deionized water, uniformly mixing, and carrying out high-pressure homogenization treatment for a plurality of times to obtain an essential oil emulsion;
s2, sucking a proper amount of essential oil emulsion into a centrifuge tube, adding a polyethyleneimine water solution, mixing, stirring, adsorbing for a period of time, and centrifuging, washing and precipitating;
s3, adding sodium carboxymethylcellulose aqueous solution, mixing, stirring, adsorbing for a period of time, and centrifuging, washing and precipitating;
s4, repeating the adsorption and washing steps to obtain the essential oil slow-release microcapsule with a multilayer core-shell structure, namely the fragrant microspheres.
7. The method for preparing a shape memory composite foaming material with fragrance according to claim 6, wherein in the step S1, the essential oil is natural plant essential oil selected from one of folium Artemisiae Argyi essential oil, Lavender essential oil, tea tree essential oil or Rose essential oil; the emulsifier is anionic surfactant selected from one or more of sodium stearate, potassium cetyl phosphate or sodium dodecyl sulfate; the concentration of the essential oil in the deionized water is 5-15%, and the emulsifier accounts for 5-10% of the mass of the essential oil; the high-pressure homogenizing pressure is 600-1200 bar, and the cycle time is 5-20 times.
8. The method for preparing the shape memory composite foaming material with fragrance according to claim 6, wherein in the step S2, the concentration of the polyethyleneimine aqueous solution is 3-10 mg/mL, and the mass ratio of the polyethyleneimine to the essential oil is (0.1-0.3): 1; the adsorption time is 5-10 min, the centrifugal rotating speed is 3000-6000 r/min, the centrifugal time is 10-40 min, and the washing times are 3-5.
9. The method for preparing a shape memory composite foaming material with fragrance according to claim 6, wherein in the step S3, the concentration of the sodium carboxymethyl cellulose aqueous solution is 1-5 mg/mL, and the mass ratio of the sodium carboxymethyl cellulose to the polyethyleneimine is (0.5-2): 1; the adsorption time is 5-10 min, the centrifugal rotating speed is 3000-6000 r/min, the centrifugal time is 10-40 min, and the washing times are 3-5.
10. The method for preparing a shape memory composite foaming material with fragrance according to claim 6, wherein in the step S4, the total number of layers of the essential oil sustained-release microcapsules is one of 2-10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210634599.9A CN114891340B (en) | 2022-06-07 | 2022-06-07 | Shape memory composite foaming material with fragrance and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210634599.9A CN114891340B (en) | 2022-06-07 | 2022-06-07 | Shape memory composite foaming material with fragrance and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114891340A true CN114891340A (en) | 2022-08-12 |
| CN114891340B CN114891340B (en) | 2024-03-08 |
Family
ID=82728831
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210634599.9A Active CN114891340B (en) | 2022-06-07 | 2022-06-07 | Shape memory composite foaming material with fragrance and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114891340B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1919445A (en) * | 2006-08-15 | 2007-02-28 | 浙江大学 | Method for preparing microcapsule by using doping porous calcium carbonate mould plates |
| CN105614641A (en) * | 2015-09-06 | 2016-06-01 | 上海应用技术学院 | Layer-by-layer self-assembled cinnamon essential oil microcapsule and preparation method thereof |
| CN108715629A (en) * | 2018-05-17 | 2018-10-30 | 滁州市赢聚高分子材料有限公司 | The special urethane raw of makeup sponge for liquid foundation |
| AU2020102627A4 (en) * | 2020-10-07 | 2020-11-26 | Agricultural Products Processing Research Institute，China Academy of Tropical Agricultural Sciences | Latex foaming sponge capable of promoting sleep and preparation method and application thereof |
| CN112592458A (en) * | 2020-12-15 | 2021-04-02 | 梦百合家居科技股份有限公司 | Polyurethane sponge with fragrance releasing and sleep aiding functions |
-
2022
- 2022-06-07 CN CN202210634599.9A patent/CN114891340B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1919445A (en) * | 2006-08-15 | 2007-02-28 | 浙江大学 | Method for preparing microcapsule by using doping porous calcium carbonate mould plates |
| CN105614641A (en) * | 2015-09-06 | 2016-06-01 | 上海应用技术学院 | Layer-by-layer self-assembled cinnamon essential oil microcapsule and preparation method thereof |
| CN108715629A (en) * | 2018-05-17 | 2018-10-30 | 滁州市赢聚高分子材料有限公司 | The special urethane raw of makeup sponge for liquid foundation |
| AU2020102627A4 (en) * | 2020-10-07 | 2020-11-26 | Agricultural Products Processing Research Institute，China Academy of Tropical Agricultural Sciences | Latex foaming sponge capable of promoting sleep and preparation method and application thereof |
| CN112592458A (en) * | 2020-12-15 | 2021-04-02 | 梦百合家居科技股份有限公司 | Polyurethane sponge with fragrance releasing and sleep aiding functions |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114891340B (en) | 2024-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101366569B1 (en) | Capsules | |
| CN109316461B (en) | Lignin wall material microcapsule based on Pickering emulsion interface crosslinking, preparation method and application in drug carrier | |
| CN103861536B (en) | Oleum Folium Artemisiae Argyi composite micro-capsule and preparation method thereof and multifunctional textile product preparation method | |
| CN102580639A (en) | Method for preparing cellulose microspheres from microfluidic chip | |
| US20210338561A1 (en) | Method for preparing microcapsule | |
| KR20150087197A (en) | Capsules | |
| CN108451925A (en) | It is a kind of to be used to carry hollow sustained-release micro-spheres of medicine and preparation method thereof | |
| JP2011231152A (en) | Method for dissolving crystalline cellulose, and method for producing porous cellulose | |
| CN101671440A (en) | Chitosan-urea resin microcapsule and synthesis method thereof | |
| CN108219394B (en) | Yellow-eliminating, whitening and brightening master batch, polyester reclaimed material and preparation method | |
| KR20240048014A (en) | Improvements in and related to organic compounds | |
| CN107973873A (en) | A kind of preparation method of super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier | |
| Wang et al. | Superelastic three-dimensional nanofiber-reconfigured spongy hydrogels with superior adsorption of lanthanide ions and photoluminescence | |
| CN114891340B (en) | Shape memory composite foaming material with fragrance and preparation method thereof | |
| US20080242765A1 (en) | Self-assembled nanofiber templates; versatile approaches for polymer nanocomposites | |
| KR101557573B1 (en) | Method for preparing controlled-release fiber and controlled-release fiber prepared thereby | |
| Luo et al. | Fragrance oil microcapsules with low content of formaldehyde: Preparation and characterization | |
| JP2023536823A (en) | improvements in or relating to organic compounds | |
| CN114097777A (en) | Double-layer drug-loaded sustained-release microcapsule and preparation method and application thereof | |
| US3753922A (en) | Production of microcapsules | |
| CN110433741A (en) | A kind of aromatic antibacterial microcapsule and preparation method thereof with carbon skeleton | |
| CN114405483B (en) | Porous cellulose microsphere adsorbent with core-shell structure, preparation method and application | |
| CN106149095A (en) | A kind of fabric lining containing hot energy storage material | |
| CN108676113B (en) | Preparation method of acid-base three-dimensional integrated yolk-shell structure micro-nano reactor | |
| CN101773811A (en) | Preparation method of hollow capsule of micro-meter scale |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |