CN106395162B - One kind flower arrangement device - Google Patents
One kind flower arrangement device Download PDFInfo
- Publication number
- CN106395162B CN106395162B CN201610791803.2A CN201610791803A CN106395162B CN 106395162 B CN106395162 B CN 106395162B CN 201610791803 A CN201610791803 A CN 201610791803A CN 106395162 B CN106395162 B CN 106395162B
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- band
- neck
- acid
- added
- piperazinedione
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
The present invention provides a kind of flower arrangement device, it is made of the spherical rubber container of band neck, band stopple and band, the band stopple fills in the band spherical rubber container neck interior of neck, and the band spherical rubber container neck external stability of neck is sleeved on by band, the band stopple top is flushed with the spherical rubber container neck top of neck；The present invention has very big advantage in terms of fresh flower packaging, fresh-keeping, transport, environmental protection.
Description
Technical field
The invention belongs to one kind flower arrangement device, more particularly it relates to arrange flowers device composition material and application.
Background technology
A kind of fresh flower is timeliness and seasonal very strong and growth conditions has certain requirements plant.The wilderness demand of fresh flower
It is the symbol of social progress and human civilization, is people's living standard quality and appreciates the important symbol that temperament and interest improves, it is deep by big
Many likes.
Fresh flower packaging is one of logistics important elements, it is the terminal of production, and the starting point of logistics, is storing, transport, selling on a commission basis
During have defencive function, quantitative function, blip facility, main purpose protect its use value, to prevent polluting or rotting
It is rotten, in order to when fresh flower is sold with higher quality.
At present, after the fresh flower manner of packing used in fresh flower shop usually first prepares the flower material that client chooses, then use
Color packing paper is wrapped from the outside, and wrapping paper and fresh flower finally are bundled into bouquet with colored ribbon.This packaging is every to have bag
Time-consuming, efficiency is low for dress, in red-letter days such as Valentine's Day, the Mother's Day, Teacher's Days, bigger, the above-mentioned packaging side of the sales volume of fresh flower
Formula can be delayed client and take colored demand at the first time.
The packaging phenomenon of " squash type " of fresh flower is more universal, and the quality of flowers product cannot be guaranteed." squash type "
Fresh flower is packed, and every goods can save the cost of transportation of dozens of yuan, but fresh flower reaches when in client's hand quality degradation, fresh flower
The proportion of goods damageds are up to more than 20%.
Fresh flower is the fresh and alive plant of ornamental value, pick follow-up supervention educate, Growth and anthesis, be the life entity by breathing, so
The fresh-keeping of fresh flower also seems especially important.
In addition, if the packaging material of fresh flower can recycle or is degradable, the protection of utilization and environment to resource has
Certain effect.
In view of the above-mentioned problems, existing there is an urgent need for one kind flower arrangement device, this combination container is in fresh flower packaging, fresh-keeping, transport, environmental protection
Aspect has very big advantage.
The content of the invention
To solve the above-mentioned problems, one aspect of the present invention provides a kind of flower arrangement device, the flower arrangement device band neck
Spherical rubber container, band stopple and band form, and the band stopple fills in the band spherical rubber container neck interior of neck, and passes through
Band is sleeved on the spherical rubber container neck external stability of neck, the band stopple top and with the spherical rubber container neck of neck
Top flushes.
In one embodiment, the spherical rubber container material of the band neck is modified polyurethane composition, band material
To expect for rubber, band stopple material be EVA foams or high-elastic PE, wherein, modified polyurethane composition is including at least polylactic acid, poly- ammonia
Ester, piperazinedione acid and expanded PTFE.
In one embodiment, the modified polyurethane composition also includes mesoporous silica.
In one embodiment, the modified polyurethane composition on polylactic acid-polyurethane copolymer by being grafted piperazine
Two ketone acids, then are blended to obtain with expanded PTFE, mesoporous silica.
In one embodiment, the grafting rate of piperazinedione acid is 1~3% on the polylactic acid-polyurethane copolymer.
In one embodiment, the grafting rate of piperazinedione acid is 1~2% on the polylactic acid-polyurethane copolymer.
In one embodiment, the top bore with the spherical rubber container of neck is 1.5~3cm, top and ball
The distance of shape upper end is 2~3cm.
In one embodiment, the width of the band is 2~3cm.
In one embodiment, a diameter of 5~8cm with stopple, thickness are 1~2cm, aperture 0.05~
0.08cm。
Device of arranging flowers described in another aspect of the present invention is applied to packing, is fresh-keeping, storing and transporting for flowers.
The above-mentioned of the application and other features, aspect and advantage is more readily understood with reference to described further below.
Brief description of the drawings
Fig. 1：The band spherical rubber container of neck
Fig. 2：Band
Fig. 3：Band stopple
Fig. 4：Arrange flowers device (1, band the spherical rubber container of neck；2nd, band；3rd, consent with holes, 4, band stopple)
Embodiment
Participate in the election of the detailed description of the invention below for being preferable to carry out method and including embodiment this hair can be more easily understood
Bright content.Unless otherwise defined, all technologies used herein and scientific terminology have common with fields of the present invention
The normally understood identical implication of technical staff.When there is a conflict, the definition in this specification shall prevail.
As used herein term " by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " comprising ",
" having ", " containing " or its any other deformation, it is intended that cover including for non-exclusionism.For example, the combination comprising listed elements
Thing, step, method, product or device are not necessarily limited to those key elements, but can include not expressly listed other key elements or
Such a composition, step, method, product or the intrinsic key element of device.
Conjunction " Consists of " excludes any key element do not pointed out, step or component.If be used in claim, this
Phrase will make claim be closed, it is not included the material in addition to the material of those descriptions, but relative normal
Except rule impurity.When being rather than immediately following in the clause that phrase " Consists of " appears in claim main body after theme,
It is only limited to the key element described in the clause；Other key elements are not excluded outside the claim as a whole.
Equivalent, concentration or other values or parameter are excellent with scope, preferred scope or a series of upper limit preferred values and lower limit
During the Range Representation that choosing value limits, this, which is appreciated that, specifically discloses by any range limit or preferred value and any scope
All scopes that any pairing of lower limit or preferred value is formed, regardless of whether the scope separately discloses.For example, when open
During scope " 1 to 5 ", described scope should be interpreted as including scope " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When number range is described herein, unless otherwise stated, otherwise the scope is intended to include its end
Value and all integers and fraction within the range.
Singulative includes plural number and object is discussed, unless the context clearly dictates otherwise." optional " or it is " any
It is a kind of " refer to that the item that describes thereafter or event may or may not occur, and the description include situation that event occurs and
The situation that event does not occur.
Approximate term in specification and claims is used for modifying quantity, represents specific the present invention is not limited to this
Quantity, further includes the modified part of the acceptable change without cause related basic function close to the quantity.Phase
Answer, modify a numerical value with " about ", " about " etc., mean that the invention is not restricted to the exact numerical.It is approximate in some examples
Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, scope limits can be with
Combine and/or exchange, these scopes include all subranges contained therebetween if not stated otherwise.
In addition, indefinite article " one kind " before key element of the present invention or component and "one" quantitative requirement to key element or component
(i.e. occurrence number) unrestriction.Therefore "one" or " one kind " should be read as including one or at least one, and odd number
The key element or component of form also include plural form, unless the obvious purport of the quantity refers to singulative.
" polymer " means by the polymerizable compound prepared by the monomer that polymerize identical or different type.Generic term
" polymer " includes term " homopolymer ", " copolymer ", " terpolymer " and " copolymer ".
" copolymer " means the polymer prepared by polymerizeing at least two different monomers.Generic term " copolymer " includes
(its is general with term " terpolymer " for term " copolymer " (its generally to refer to the polymer prepared by two kinds of different monomers)
To refer to the polymer prepared by three kinds of different monomers).It is also included by polymerizeing more kinds of monomers the polymer that manufactures.
" blend " means that two or more polymer mixes the polymer to be formed by physics or chemical method jointly.
One aspect of the present invention provides a kind of flower arrangement device, the spherical rubber container of the flower arrangement device band neck, with holes
Plug and band composition, the band stopple fills in the band spherical rubber container neck interior of neck, and is sleeved on band neck ball by band
Shape rubber container neck external stability, the band stopple top are flushed with the spherical rubber container neck top of neck.
In one embodiment, the spherical rubber container material of the band neck is modified polyurethane composition, band material
To expect for rubber, band stopple material be EVA foams or high-elastic PE, wherein, modified polyurethane composition is including at least polylactic acid, poly- ammonia
Ester, piperazinedione acid and expanded PTFE.
In one embodiment, the modified polyurethane composition also includes mesoporous silica.
In one embodiment, the modified polyurethane composition on polylactic acid-polyurethane copolymer by being grafted piperazine
Two ketone acids, then are blended to obtain with expanded PTFE, mesoporous silica.
In one embodiment, the grafting rate of piperazinedione acid is 1~3% on the polylactic acid-polyurethane copolymer.
In one embodiment, the grafting rate of piperazinedione acid is 1~2% on the polylactic acid-polyurethane copolymer.
Polyurethane (Polyurethane, PU) has the carbamate (- NHCOO-) unit repeated, except containing substantial amounts of
, may be also containing hydrogen bond between ester group, ether, urea groups and macromolecular etc. in structure outside carbamate groups.PU usually by
Polyalcohol (polyester polyol or polyether polyol), diisocyanate and chain extender polycondensation synthesize, and can be divided into its structure soft
Section and hard section two parts, soft segment is made of polyester or/and polyethers, and hard section is into packet by epoxide formic acid esters, chain extender etc.
Into, thus structure type can be seen that PU is a kind of linear block polymer, the formation of soft segment and hard section and its respective heat
Mechanics incompatibility is related, due to there are different thermodynamics incompatibilities, the soft segment in polymer flock together to be formed it is soft
Duan Xiang, hard section flock together to form hard section phase again, and microphase-separated then occurs.Phase separation degree between soft, hard section passes through hard
Oxygen key amount between section and hard section is as can be seen, and soft, hard section the degree that mixes can be by the oxygen key amount between hard section and soft segment
Find out.The hard section of polyurethane mutually plays the role of physical crosslinking in the base, and soft segment is crosslinked by hard section phase region, is polyurethane
Pliability provides necessary condition, just because of the micro phase separation structure of polyurethane uniqueness so that its with excellent elasticity,
The advantages that tensile property, wearability and low clean crystalline substance are spent, and structure is easy to process and designs.
Polylactic acid (Polylacticacid, PLA) is also referred to as polylactide, is to be formed with lactic acid (LA) for main monomer polymerization
Polymer, the raw material of lactic acid is starch, and by being extracted in the plants such as corn, wheat, starch has obtained Portugal after enzyme decomposes
Grape sugar, recycling the role transformation of lactobacillus-fermented becomes PLA, is a kind of tunning of microorganism.It can be seen that this raw material
It is rich and easy to get and renewable, the dependence to petrochemical industry is substantially reduced, is conducive to environmental protection.According to it is optically active not
Together, lactic acid can be divided into D-lactic acid and L-lactic acid, and the racemic being made of equivalent d-isomer and levo form) lactic acid, phase
Ying Di, polylactic acid also have these three basic stereoisomers of poly- L-lactic acid, Poly L-lactic acid and ploy DL lactic caid, wherein a poly- left side
Rotation lactic acid and ploy DL lactic caid are easier to obtain.
PLA is a kind of typical biodegradable aliphatic polyester, its final product degraded is pollution-free, non-hazardous
H2O and CO2, various products using convenient post-treatment, environmental protection, have it is nontoxic, nonirritant, also with certain biocompatibility,
It is widely applied to biomedicine field.The mechanical performance of polylactic acid is good with physical property, and antibacterial and mouldproof, plasticization is processed into
Type, prospect is all had a vast market in all various aspects such as industrial and civilian plastics, packaging, amenities, fabric.
PLA is a kind of aliphatic polyester, and ester bond is contained in molecular structure, and facile hydrolysis, makes it have good degradation property,
Final catabolite is H2O and CO2, to environment non-hazardous.The degraded of PLA can be divided into two classes:(1) simple hydrolysis is degraded, principle
For the ester bond in water molecules attack PLA strands, ester bond is in H+The lower fracture of effect, macromolecular chain are disconnected, are degraded to water-soluble
Lactic acid monomer, and then be decomposed into carboxylic acid (end carboxyl) and alcohol, the catabolite containing end carboxyl is generally trapped in PLA products
Portion, can be produced from acceleration effect, so it has been generally acknowledged that the inside degradation rate of PLA products, which is more than superficial degradation speed, research table
Bright, the PDLLA of non-crystalline is more easy to hydrolytic degradation compared to the PLLA of crystalline state；(2) microorganism and ferment degraded:This method is
The degradation model of most important degradation material in nature, enzyme in nature cannot directly attack PLA, but first allow PLA
Hydrolyze, rupture its strand, molecular weight reduces, and then receives the attack of enzyme, further degraded.Polymerization not soluble in water
The process that thing is changed into water-soluble substances in vivo is known as molten candle effect.Macroscopically see, corrosion process shows as the structure quilt of sample
Destroy, volume diminishes, and is broken into fragment, loses original mechanical strength, and overall structure modification is weightless, final degradable and quilt
Absorption of human body excludes external；See on microcosmic and reduced rapidly as polymer macromolecule chain break, molecular weight, become small molecule
And body fluid is dissolved in, gulped down by cell and instigate and convert, be metabolized the degraded of PLA and show as procedure below:In PLA molecules after a large amount of water suctions,
The ester linkage breaking in macromolecular chain is caused, is hydrolyzed, then solable matter is constantly spread, and PLA sample bursts produce fragment,
Subsequent fragment is dissolved with the time.
The soft segment of modified polyurethane is made of biodegradable aliphatic polyesters such as polylactic acid, polycaprolactones, hard section then by
Aliphatic (such as isophorone diisocyanate) or alicyclic diisocyanate and small molecule glycol composition, thus obtain degradable
, avirulent polyurethane.Since the Ester of this kind of polyurethane soft segment is typically to be synthesized with small-molecule substance, and it is easy to water
Solution, can also become small molecule after hydrolysis.
The basic structure of diketopiperazine compound is the Cyclic dipeptides formed by two amino acid condensations, because its skeleton has
Stable six-membered ring structure, and have two hydrogen-bond donors and two hydrogen bond receptors so that DKPs have stronger bioactivity and
Pharmacological activity, becomes an important pharmacophore in pharmaceutical chemistry.A series of rings two are found from marine microorganism in recent years
Peptides, research shows that its function is not limited to antibacterial, cytotoxic activity etc., in quorum sensing regulatory mechanism
It act as the key player of signaling molecule.
Piperazine ring is common aza ring in pharmaceutical chemistry research, and piperazine ring is introduced in drug molecule effectively to be adjusted
The physicochemical property of nodal compound, improves the pharmacokinetic property of medicine, and much the compound containing piperazine ring is shown strong
Antifungal activity, a series of derivatives that chain amino is modified with piperazine ring show good antifungic action, show wide resist
Fungi is composed, and has good inhibition to bacteriums such as bacillus subtilises.
In the present invention, piperazinedione acid has hay bacillus, Pseudomonas fluorescence and staphylococcus aureus etc.
Certain inhibitory action, can extend the fresh keeping time of fresh flower.
Expanded PTFE (expanded Polytetrafluoroethylene, abbreviation e-PTFE) is a kind of new
Environmentally protective high molecular material, is widely used in the fields such as clothes, building, electronics, chemical industry medical treatment.It is by polytetrafluoroethylene (PTFE)
(PTFE) it is prepared through stretch processes, forms the duct of about 0.1~1.5 μm of rank, porosity is up to 82%.e-
PTFE inherits the advantages of PTFE, has microcosmic net structure, the extremely excellent resistance to chemical corrosion of " microfibre-node ",
Anti-aging property, low-surface-energy, insulation performance and fire resistance.Micron level duct possessed by it, can effectively stop liquid
State water and solid dust pass through, and have an excellent functions of waterproof and dustproof, and high voidage can allow air and water vapour point again
Son passes through, and has the function of good water proof and dust proof and air-moisture-permeable, therefore e-PTFE is most promising forth generation
Waterproof and breathable product.
Mesoporous silica is using organic matter as template, is synthesized by the interfacial assembly between template and inorganic species
Have narrow pore size distribution, the inorganic porous material of pore passage structure rule.
Compared with traditional porous material, orderly poromerics is mainly characterized by:
(l) has well-regulated pore passage structure；
(2) pore-size distribution is very narrow, and can be adjusted between 1.3 1 2nm；
(3) pass through optimum synthesis condition or post processing, can have good heat endurance and hydrothermal stability；
(4) particle has well-regulated shape；
(5) duct shape and aperture size can be controlled by selecting the surfactant of different structure, and can be micro-
The duct order of height is kept in metrical scale.
The preparation method of mesoporous silica is as follows：
By the C of 2mol2-8-2Surfactant and 10mol Na2SiO3·9H2O, is dissolved in the deionized water of 30.0ml respectively
In, two kinds of solution are mixed rapidly in the case of being then stirred at room temperature, after twenty minutes, are instilled dropwise in the case of stirring
The sulfuric acid solution of 3mol/L, reconciles PH between 9-10, mixed liquor stands 5h at room temperature, then the constant temperature 3 in 80 DEG C of baking oven
My god, obtained solid precipitation is filtered, is dried in atmosphere after washing, obtains organic/inorganic combination product.Product with 1.5 DEG C/
The speed of min is heated to 540 DEG C in atmosphere, the product that constant temperature 6h is roasted.
The characterization of mesoporous silica：
Using Barertt-Joyner-Halenda (BJH) model analysis aperture, the aperture of the sample of synthesis is in 1.5nm
Left and right.
The preparation method of modified polyurethane composition is as follows：
(1) 1 mole of 1,4- butanediol (BDO) and 4 moles of hexamethylene diisocyanates (HDI) are added to 250ml tri-
In mouthful flask, be warming up to 80 DEG C of reaction 5h, after react, be cooled to room temperature, reaction product is transferred in beaker, addition just oneself
Alkane cleans, and stirs 5min with glass bar, is completely dispersed solid product, filter, repeats aforesaid operations three times, it is ensured that in product
Unreacted hexamethylene diisocyanate has cleaned up.30 DEG C of solid product after cleaning is dried under vacuum to constant weight.It is dry
Dissolved after dry with DMSO stand-by (per 100mL DMSO dissolving 20g HDI-BDO-HDI chain extenders)；
(2) 100ml PEG-600 are added in vacuum reaction bottle, the vaccum dewatering 2h under the conditions of 90 DEG C, cools down after water removal
To room temperature, then 1mol L- lactides and 1.1mol caprolactones are added into vacuum reaction bottle, add octoate catalyst stannous
(catalyst quality accounts for the 0.5% of reaction raw materials gross mass), it is after vacuumizing that vacuum reaction bottle is closed, it is anti-under the conditions of 140 DEG C
24h is answered to prepare prepolymer.After the completion of reaction, prepolymer is cooled to 80 DEG C, adds the PEG-600 after 60ml vaccum dewaterings, stirring
After uniformly, the DMSO solution of HDI-BDO-HDI chain extenders is added dropwise dropwise.After being added dropwise to complete, 5h is reacted at 80 DEG C.Reaction process
In, reactant viscosity can increase, and can suitably add some solvent dioxane.The solution for reacting completion is poured slowly into deionization
Settle, filter in water, products therefrom is dried into 48h in vacuum drying chamber, be polylactic acid-polyurethane copolymer；
(3) polylactic acid-polyurethane copolymer is immersed into 2V 2vt% acetums and the hydrogenperoxide steam generator of 2V 5wt%
In, it is slowly added to be dissolved in sour (0.5g) solution of piperazinedione of 5ml methanol, after the reaction was complete, with 10wt%NaOH aqueous solutions
Adjusting after pH is in neutrality and filter, washing soaking to trapped substance, filter, and products therefrom is dried 48h in vacuum drying chamber,
As piperazinedione acid polydactyl acid-polyurethane copolymer；
(4) piperazinedione acid polydactyl acid-polyurethane copolymer is added into three-necked flask, is warming up to 120 DEG C, solid
In molten condition, 1g expanded polytetrafluoroethylsealing particles are added, stir 0.5h, 1g mesoporous silica particles is added, is stirred for 1h,
Solid is in molten condition vacuumizing and defoaming, immediately pours into mould uniformly mixed mixture, mould is put into 100 DEG C of baking
Heat 2h in case, rise cures 2h to 120 DEG C again for box temperature degree, demoulds, that is, obtains spherical rubber container.
The size in modified polyurethane aperture is observed by SEM, finds modified polyurethane composition aperture in 0.3~0.4nm.
The micron level duct that expanded PTFE and mesoporous silica have, can effectively stop liquid water and consolidate
Body dust passes through, and has excellent functions of waterproof and dustproof, and high voidage can allow air and water vapour molecule smoothly to lead to again
Cross, there is good airing function, both act synergistically, and improve the size in modified polyurethane aperture, improve modified polyurethane
The waterproof and breathable function of composition.
The aperture of air hole is more than 0.33nm, and less than 0.4nm, i.e. the aperture of air hole is more than oxygen molecule and carbon dioxide
The diameter of molecule, less than the diameter of hydrone so that oxygen and carbon dioxide molecule can be by, and hydrone can not be by, from
And realize air permeable waterproof.
In one embodiment, the number-average molecular weight of the expanded PTFE is 5000~30000；Preferably,
The number-average molecular weight of the expanded PTFE is 8000~20000.
Number-average molecular weight is measured based on film osmosis.
Membrane osmotic pressure method is using two capillaries, two infiltration connection ponds, the device that centre is separated with pellicle AB, infiltration
While containing Polymer Solution, solvent is contained in another side in pond.The pore size of pellicle allows solvent molecule freely to pass through, and solute point
Sub-volume is big, cannot pass through pellicle.When infiltration starts, the quantity that solvent molecule enters solution pool by pellicle is more than solution
Solvent molecule enters the quantity of solvent cell by pellicle in pond.Solution concentration is gradually diluted, the capillary on solution pool one side
Liquid level gradually rises, and when system reaches thermodynamic equilibrium class hour, the capillary liquid-column height difference of solution pool and solvent cell reaches certain value,
The two pond solvent molecules quantity that interpenetrates reaches dynamic equilibrium, at this moment the pressure of the difference, i.e. solvent column of two capillary liquid-column heights
Force difference is the osmotic pressure π of solution.
π=△ hD (1)
In formula:△ h are the difference (cm) of capillary liquid-column height；D is the density (g/mL) of solvent.The infiltration of perfect solution
Pressure is represented by with Van't Hoff (Vant Hoff) two laws:
π=NRT/V=RTC/Mn (2)
In formula：V-liquor capacity, molal quantity of the N-solute in V, the number-average molecular weight of Mn-solute, C-solution
Concentration (g/100mL), R-constant, 848.4；T-operation absolute temperature.
By (1), (2) formula obtains Δ hD=RTC/Mn
Mn=RT/ [(Δ h/c) D]
Δ h is that Δ h c claim reduced osmotic pressure from the Δ h values numerically read.
Van't Hoff's law could be set up only in perfect solution in the solution of infinite dilution, that is,:
Mn=RT/ (Δ h/c) c=0D (3)
So trying to achieve (Δ h/c) c=0 using extrapolation, that is, a series of macromolecule polymer solution of various concentrations is prepared,
Its Δ h values are measured respectively, then using concentration c as abscissa, using Δ h/c as ordinate, draw a straight line and the straight line c=that extrapolates
Intercept Δ h/c at 0 substitutes into (3) formula, can try to achieve the number-average molecular weight of high polymer.
Rubber has the strong flexible polymer material of reversible deformation.High resilience at room temperature, acts in the external force of very little
It is lower to produce compared with large deformation, remove resilient after external force.Rubber belongs to entirely without styling polymer, its glass transition
Temperature (Tg) is low, and molecular weight is often very big, more than hundreds of thousands.The strand of rubber can be crosslinked, and the rubber after crosslinking is by external force
When effect deforms, there is the ability restored rapidly, and there is good physical and mechanical property and chemical stability.Rubber is
The base stock of rubber industry, is widely used in manufacture tire, sebific duct, adhesive tape, cable and other various rubbers.
Foam is divided into PU foams, antistatic foam, conducting foam, EPE, antistatic EPE, PORON, CR, EVA, bridge formation PE,
SBR, EPDM etc., have the characteristics that easy to use, bending freely, the ultra-thin, dependable performance of volume etc. it is a series of.
Foam has following feature：(1) the extraordinary shield effectiveness of low-pressure, shield effectiveness is more than 90dB；(2) there is bullet
It is property, light-weight.(3) anticorrosion nickel coating can cathodic protection；(4) low surface contacted resistance；(5) quick pressure-sensitive fixation；(6)
Client can refer to measured length；(7) numerous section selections；(8) UL grades of fire prevention.
Foam product with stable quality, resistance to hot pressing is not easily to fall off, and tension intensity is high, after product installation, through -20 DEG C of low temperature
To 80 DEG C of high temperature, loop cycle test 72 still keeps this quality when small.With easy to use, bending freely, volume is ultra-thin, performance
A series of features such as reliable.
EVA resin is ethylene-vinyl acetate copolymer, and general vinyl acetate (VA) content is 5%~40%.With polyethylene
Compare, EVA in strand due to introducing vinyl acetate monomer, so as to reduce high-crystallinity, improves pliability, anti-impact
Hitting property, filler intermiscibility and heat sealing performance, are widely used in foaming shoe material, functional greenhouse film, packaging film, hot melt adhesive, electricity
The field such as line cable and toy.
EVA products of rubber and plastic are novel environment friendly plastics expanded materials, have good buffering, antidetonation, heat-insulated, moisture-proof, anti-ization
Learn corrosion the advantages that, and it is nontoxic, do not absorb water.
In one embodiment, the top bore with the spherical rubber container of neck is 1.5~3cm, top and ball
The distance of shape upper end is 2~3cm.
In one embodiment, the width of the band is 2~3cm.
In one embodiment, a diameter of 5~8cm with stopple, thickness are 1~2cm, aperture 0.05~
0.08cm。
In the present invention, modified polyurethane composition includes at least polylactic acid, polyurethane, piperazinedione acid and e-PTFE
Ethene, mesoporous silica；By polylactic acid, piperazinedione acid modified polyurethane, then with expanded PTFE and micropore
Silica dioxide granule, which carries out the modified polyurethane composition that blending is prepared, has the function of environmental protection, waterproof and breathable and sterilization,
Can ensure the plants such as flowers pick follow-up supervention educate, the effect of Growth and anthesis.
In addition contain ester bond in modified polyurethane composition molecular structure in the present invention, its with good degradation property,
Final catabolite is H2O and CO2, to environment non-hazardous, therefore modified polyurethane composition not only has excellent elasticity, draws
Stretch the advantages that performance, wearability and low clean crystalline substance are spent, and structure is easy to process and design, pack efficient and convenient during fresh flower, it is ventilative
Waterproof, antibacterial effective efficiency help the plants such as flowers during fresh flower transports and stores and educate, grow picking follow-up supervention
Bloom, moreover, when modified polyurethane composition breakage cannot reuse, its is degradable, and environment will not be polluted.
Device of arranging flowers described in another aspect of the present invention is applied to packing, is fresh-keeping, storing and transporting for flowers.
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiments are only used
In the invention will be further described, it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field
Some the nonessential modifications and adaptations made according to the content of the invention described above, still fall within protection scope of the present invention.
In addition, if without other explanations, it is raw materials used to be all commercially available, it is purchased from traditional Chinese medicines chemical reagent.
A1：Polyurethane
Preparation method is as follows：(1) by 1 mole of 1,4-butanediol (BDO) and 4 moles of hexamethylene diisocyanates (HDI),
It is added in 500ml three-necked flasks, is warming up to 80 DEG C of reaction 5h, after having reacted, is cooled to room temperature, reaction product is transferred to burning
In cup, n-hexane cleaning is added, 5min is stirred with glass bar, is completely dispersed solid product, filter, repeat aforesaid operations three
It is secondary, it is ensured that unreacted hexamethylene diisocyanate has cleaned up in product.By 30 DEG C of vacuum of solid product after cleaning
Drying obtains base polyurethane prepolymer for use as to constant weight；
(2) triethylene glycol (mass ratio of triethylene glycol and performed polymer is 3%) is added in above-mentioned performed polymer, be warming up to
75 DEG C of reaction 2.5h；
(3) polymer in step (2) is warming up to 120 DEG C, solid is in molten condition vacuumizing and defoaming, will be mixed immediately equal
Even mixture is poured into mould, and mould is put into 100 DEG C of baking oven and heats 2h, and rise is cured to 120 DEG C again for box temperature degree
2h, the demoulding, that is, obtain spherical rubber container.
A2：Polylactic acid-polyurethane copolymer
Preparation method is as follows：(1) by 1 mole of 1,4- butanediol (BDO) and 4 moles of hexamethylene diisocyanates (HDI)
It is added in 500ml three-necked flasks, is warming up to 80 DEG C of reaction 5h, after having reacted, is cooled to room temperature, reaction product is transferred to burning
In cup, n-hexane cleaning is added, 5min is stirred with glass bar, is completely dispersed solid product, filter, repeat aforesaid operations three
It is secondary, it is ensured that unreacted hexamethylene diisocyanate has cleaned up in product.By 30 DEG C of vacuum of solid product after cleaning
Dry to constant weight.Dissolved after drying with DMSO stand-by (per 100mL DMSO dissolving 20g HDI-BDO-HDI chain extenders)；
(2) a certain amount of 100ml PEG-600 are added in vacuum reaction bottle, the vaccum dewatering 2h under the conditions of 90 DEG C, water removal
After be cooled to room temperature, then 1mol L- lactides and 1.1mol caprolactones are added into vacuum reaction bottle, add octoate catalyst
Stannous (catalyst quality accounts for the 0.5% of reaction raw materials gross mass), it is after vacuumizing that vacuum reaction bottle is closed, in 140 DEG C of conditions
Lower reaction 24h prepares prepolymer, and after the completion of reaction, prepolymer is cooled to 80 DEG C, adds the PEG-600 after 60ml vaccum dewaterings,
After stirring evenly, the DMSO solution of HDI-BDO-HDI chain extenders is added dropwise dropwise.After being added dropwise to complete, 5h is reacted at 80 DEG C.Reacted
Cheng Zhong, reactant viscosity can increase, and can suitably add some solvent dioxane.By react complete solution be poured slowly into from
Settle, filter in sub- water, products therefrom is dried into 48h in vacuum drying chamber, be polylactic acid-polyurethane copolymer；
(3) polymer in step (2) is warming up to 120 DEG C, solid is in molten condition vacuumizing and defoaming, will be mixed immediately equal
Even mixture is poured into mould, and mould is put into 100 DEG C of baking oven and heats 2h, and rise is cured to 120 DEG C again for box temperature degree
2h, the demoulding, that is, obtain spherical rubber container.
A3：It is grafted polylactic acid-polyurethane copolymer of piperazinedione acid (piperazinedione acid grafting rate is 2%)
Preparation method is as follows：(1) by 1 mole of 1,4- butanediol (BDO) and 4 moles of hexamethylene diisocyanates (HDI)
It is added in 500ml three-necked flasks, is warming up to 80 DEG C of reaction 5h, after having reacted, is cooled to room temperature, reaction product is transferred to burning
In cup, n-hexane cleaning is added, 5min is stirred with glass bar, is completely dispersed solid product, filter, repeat aforesaid operations three
It is secondary, it is ensured that unreacted hexamethylene diisocyanate has cleaned up in product.By 30 DEG C of vacuum of solid product after cleaning
Dry to constant weight.Dissolved after drying with DMSO stand-by (per 100mL DMSO dissolving 20g HDI-BDO-HDI chain extenders)；
(2) a certain amount of 100ml PEG-600 are added in vacuum reaction bottle, the vaccum dewatering 2h under the conditions of 90 DEG C, water removal
After be cooled to room temperature, then 1mol L- lactides and 1.1mol caprolactones are added into vacuum reaction bottle, add octoate catalyst
Stannous (catalyst quality accounts for the 0.5% of reaction raw materials gross mass), it is after vacuumizing that vacuum reaction bottle is closed, in 140 DEG C of conditions
Lower reaction 24h prepares prepolymer.After the completion of reaction, prepolymer is cooled to 80 DEG C, adds the PEG-600 after 60ml vaccum dewaterings,
After stirring evenly, the DMSO solution of HDI-BDO-HDI chain extenders is added dropwise dropwise.After being added dropwise to complete, 5h is reacted at 80 DEG C.Reacted
Cheng Zhong, reactant viscosity can increase, and can suitably add some solvent dioxane.By react complete solution be poured slowly into from
Settle, filter in sub- water, products therefrom is dried into 48h in vacuum drying chamber, be polylactic acid-polyurethane copolymer；
(3) polylactic acid-polyurethane copolymer is immersed into 2V 2vt% acetums and the hydrogenperoxide steam generator of 2V 5wt%
In, it is slowly added to be dissolved in sour (0.5g) solution of piperazinedione of 5ml methanol, after the reaction was complete, with 10wt%NaOH aqueous solutions
Adjusting after pH is in neutrality and filter, washing soaking to trapped substance, filter, and products therefrom is dried 48h in vacuum drying chamber,
As piperazinedione acid polydactyl acid-polyurethane copolymer；
(4) polymer in step (3) is warming up to 120 DEG C, solid is in molten condition vacuumizing and defoaming, will be mixed immediately equal
Even mixture is poured into mould, and mould is put into 100 DEG C of baking oven and heats 2h, and rise is cured to 120 DEG C again for box temperature degree
2h, the demoulding, that is, obtain spherical rubber container.
A4：It is grafted the composition that polylactic acid-polyurethane copolymer of piperazinedione acid and tetrafluoroethene particle are blended
(tetrafluoroethene particle pore size is 2 μm, and number-average molecular weight 10000,2%) piperazinedione acid grafting rate is
Preparation method is as follows：(1) by 1 mole of 1,4- butanediol (BDO) and 4 moles of hexamethylene diisocyanates (HDI)
It is added in 500ml three-necked flasks, is warming up to 80 DEG C of reaction 5h, after having reacted, is cooled to room temperature, reaction product is transferred to burning
In cup, n-hexane cleaning is added, 5min is stirred with glass bar, is completely dispersed solid product, filter, repeat aforesaid operations three
It is secondary, it is ensured that unreacted hexamethylene diisocyanate has cleaned up in product.By 30 DEG C of vacuum of solid product after cleaning
Dry to constant weight.Dissolved after drying with DMSO stand-by (per 100mL DMSO dissolving 20g HDI-BDO-HDI chain extenders)；
(2) a certain amount of 100ml PEG-600 are added in vacuum reaction bottle, the vaccum dewatering 2h under the conditions of 90 DEG C, water removal
After be cooled to room temperature, then 1mol L- lactides and 1.1mol caprolactones are added into vacuum reaction bottle, add octoate catalyst
Stannous (catalyst quality accounts for the 0.5% of reaction raw materials gross mass), it is after vacuumizing that vacuum reaction bottle is closed, in 140 DEG C of conditions
Lower reaction 24h prepares prepolymer.After the completion of reaction, prepolymer is cooled to 80 DEG C, adds the PEG-600 after 60ml vaccum dewaterings,
After stirring evenly, the DMSO solution of HDI-BDO-HDI chain extenders is added dropwise dropwise.After being added dropwise to complete, 5h is reacted at 80 DEG C.Reacted
Cheng Zhong, reactant viscosity can increase, and can suitably add some solvent dioxane.By react complete solution be poured slowly into from
Settle, filter in sub- water, products therefrom is dried into 48h in vacuum drying chamber, be polylactic acid-polyurethane copolymer；
(3) polylactic acid-polyurethane copolymer is immersed into 2V 2vt% acetums and the hydrogenperoxide steam generator of 2V 5wt%
In, it is slowly added to be dissolved in sour (0.5g) solution of piperazinedione of 5ml methanol, after the reaction was complete, with 10wt%NaOH aqueous solutions
Adjusting after pH is in neutrality and filter, washing soaking to trapped substance, filter, and products therefrom is dried 48h in vacuum drying chamber,
As piperazinedione acid polydactyl acid-polyurethane copolymer；
(4) piperazinedione acid polydactyl acid-polyurethane copolymer is added into three-necked flask, is warming up to 120 DEG C, solid
In molten condition, 2g polytetrafluoroethylgranule granules are added, stir 0.5h, solid is in molten condition vacuumizing and defoaming, immediately will mixing
Uniform mixture is poured into mould, and mould is put into 100 DEG C of baking oven and heats 2h, rise for box temperature degree to 120 DEG C it is ripe again
Change 2h, the demoulding, that is, obtain spherical rubber container.
A5：It is grafted the group that polylactic acid-polyurethane copolymer of piperazinedione acid and varicosity tetrafluoroethene particle are blended
(varicosity tetrafluoroethene particle pore size is 0.2 μm to compound, and number-average molecular weight 10000,2%) piperazinedione acid grafting rate is
Preparation method is as follows：(1) by 1 mole of 1,4- butanediol (BDO) and 4 moles of hexamethylene diisocyanates (HDI)
It is added in 500ml three-necked flasks, is warming up to 80 DEG C of reaction 5h, after having reacted, is cooled to room temperature, reaction product is transferred to burning
In cup, n-hexane cleaning is added, 5min is stirred with glass bar, is completely dispersed solid product, filter, repeat aforesaid operations three
It is secondary, it is ensured that unreacted hexamethylene diisocyanate has cleaned up in product.By 30 DEG C of vacuum of solid product after cleaning
Dry to constant weight.Dissolved after drying with DMSO stand-by (per 100mL DMSO dissolving 20g HDI-BDO-HDI chain extenders)；
(2) a certain amount of 100ml PEG-600 are added in vacuum reaction bottle, the vaccum dewatering 2h under the conditions of 90 DEG C, water removal
After be cooled to room temperature, then 1mol L- lactides and 1.1mol caprolactones are added into vacuum reaction bottle, add octoate catalyst
Stannous (catalyst quality accounts for the 0.5% of reaction raw materials gross mass), it is after vacuumizing that vacuum reaction bottle is closed, in 140 DEG C of conditions
Lower reaction 24h prepares prepolymer.After the completion of reaction, prepolymer is cooled to 80 DEG C, adds the PEG-600 after 60ml vaccum dewaterings,
After stirring evenly, the DMSO solution of HDI-BDO-HDI chain extenders is added dropwise dropwise.After being added dropwise to complete, 5h is reacted at 80 DEG C.Reacted
Cheng Zhong, reactant viscosity can increase, and can suitably add some solvent dioxane.By react complete solution be poured slowly into from
Settle, filter in sub- water, products therefrom is dried into 48h in vacuum drying chamber, be polylactic acid-polyurethane copolymer；
(3) polylactic acid-polyurethane copolymer is immersed into 2V 2vt% acetums and the hydrogenperoxide steam generator of 2V 5wt%
In, it is slowly added to be dissolved in sour (0.5g) solution of piperazinedione of 5ml methanol, after the reaction was complete, with 10wt%NaOH aqueous solutions
Adjusting after pH is in neutrality and filter, washing soaking to trapped substance, filter, and products therefrom is dried 48h in vacuum drying chamber,
As piperazinedione acid polydactyl acid-polyurethane copolymer；
(4) piperazinedione acid polydactyl acid-polyurethane copolymer is added into three-necked flask, is warming up to 120 DEG C, solid
In molten condition, 2g expanded polytetrafluoroethylsealing particles are added, stir 0.5h, solid is in molten condition vacuumizing and defoaming, immediately will
Uniformly mixed mixture is poured into mould, and mould is put into 100 DEG C of baking oven and heats 2h, and rise is for box temperature degree to 120 DEG C
2h is cured again, is demoulded, that is, is obtained spherical rubber container.
A6：It is grafted the composition (two that polylactic acid-polyurethane copolymer of piperazinedione acid and silica dioxide granule mix
Silica pore size 10nm；2%) piperazinedione acid grafting rate is
Preparation method is as follows：
(1) silica dioxide granule:By the Transition metal salt ZnCl of 0.3g2Being added to 100mL substance withdrawl syndromes is
In the dilute hydrochloric acid solution of 2mol/L, metal salt is set to be dissolved completely in aqueous solution with magnetic agitation in 35 DEG C of steady temperatures, so
2.5g nonionic surfactant ether oxygen class surfactants P123 is added in backward above-mentioned system.In 35 DEG C of constant temperature, magnetic force stirs
Mix 3 it is small when, afterwards into above-mentioned system be added dropwise 5.6mL tetraethyl orthosilicates (TEOS), continue afterwards stirring 6 it is small when, at room temperature
Stand 24 it is small when, pour out supernatant, remaining white depositions be transferred in crucible.Finally when calcining 3 is small under the conditions of 550 DEG C
(batch-type furnace 5 DEG C of heating per minute).
(2) 1 mole of 1,4- butanediol (BDO) and 4 moles of hexamethylene diisocyanates (HDI) are added to 500ml tri-
In mouthful flask, be warming up to 80 DEG C of reaction 5h, after react, be cooled to room temperature, reaction product is transferred in beaker, addition just oneself
Alkane cleans, and stirs 5min with glass bar, is completely dispersed solid product, filter, repeats aforesaid operations three times, it is ensured that in product
Unreacted hexamethylene diisocyanate has cleaned up, and 30 DEG C of solid product after cleaning is dried under vacuum to constant weight, does
Dissolved after dry with DMSO stand-by (per 100mL DMSO dissolving 20g HDI-BDO-HDI chain extenders)；
(3) a certain amount of 100ml PEG-600 are added in vacuum reaction bottle, the vaccum dewatering 2h under the conditions of 90 DEG C, water removal
After be cooled to room temperature, then 1mol L- lactides and 1.1mol caprolactones are added into vacuum reaction bottle, add octoate catalyst
Stannous (catalyst quality accounts for the 0.5% of reaction raw materials gross mass), it is after vacuumizing that vacuum reaction bottle is closed, in 140 DEG C of conditions
Lower reaction 24h prepares prepolymer.After the completion of reaction, prepolymer is cooled to 80 DEG C, adds the PEG-600 after 60ml vaccum dewaterings,
After stirring evenly, the DMSO solution of HDI-BDO-HDI chain extenders is added dropwise dropwise.After being added dropwise to complete, 5h is reacted at 80 DEG C.Reacted
Cheng Zhong, reactant viscosity can increase, and can suitably add some solvent dioxane.By react complete solution be poured slowly into from
Settle, filter in sub- water, products therefrom is dried into 48h in vacuum drying chamber, be polylactic acid-polyurethane copolymer；
(4) polylactic acid-polyurethane copolymer is immersed into 2V 2vt% acetums and the hydrogenperoxide steam generator of 2V 5wt%
In, it is slowly added to be dissolved in sour (0.5g) solution of piperazinedione of 5ml methanol, after the reaction was complete, with 10wt%NaOH aqueous solutions
Adjusting after pH is in neutrality and filter, washing soaking to trapped substance, filter, and products therefrom is dried 48h in vacuum drying chamber,
As piperazinedione acid polydactyl acid-polyurethane copolymer；
(5) piperazinedione acid polydactyl acid-polyurethane copolymer is added by weight into three-necked flask, is warming up to
120 DEG C, solid is in molten condition, adds 2g silica dioxide granules, is stirred for 1h, and solid is in molten condition vacuumizing and defoaming, is stood
The mixture that will be uniformly mixed is poured into mould, and mould is put into 100 DEG C of baking oven and heats 2h, and rise supplies box temperature degree extremely
120 DEG C cure 2h again, and the demoulding, that is, obtain spherical rubber container.A7：It is grafted polylactic acid-polyurethane copolymer of piperazinedione acid
Composition (the mesoporous silica particles pore size 1.5nm mixed with mesoporous silica particles；Piperazinedione acid grafting
2%) rate is
Preparation method is as follows：(1) by 1 mole of 1,4- butanediol (BDO) and 4 moles of hexamethylene diisocyanates (HDI)
It is added in 500ml three-necked flasks, is warming up to 80 DEG C of reaction 5h, after having reacted, is cooled to room temperature, reaction product is transferred to burning
In cup, n-hexane cleaning is added, 5min is stirred with glass bar, is completely dispersed solid product, filter, repeat aforesaid operations three
It is secondary, it is ensured that unreacted hexamethylene diisocyanate has cleaned up in product.By 30 DEG C of vacuum of solid product after cleaning
Dry to constant weight.Dissolved after drying with DMSO stand-by (per 100mL DMSO dissolving 20g HDI-BDO-HDI chain extenders)；
(2) a certain amount of 100ml PEG-600 are added in vacuum reaction bottle, the vaccum dewatering 2h under the conditions of 90 DEG C, water removal
After be cooled to room temperature, then 1mol L- lactides and 1.1mol caprolactones are added into vacuum reaction bottle, add octoate catalyst
Stannous (catalyst quality accounts for the 0.5% of reaction raw materials gross mass), it is after vacuumizing that vacuum reaction bottle is closed, in 140 DEG C of conditions
Lower reaction 24h prepares prepolymer.After the completion of reaction, prepolymer is cooled to 80 DEG C, adds the PEG-600 after 60ml vaccum dewaterings,
After stirring evenly, the DMSO solution of HDI-BDO-HDI chain extenders is added dropwise dropwise.After being added dropwise to complete, 5h is reacted at 80 DEG C.Reacted
Cheng Zhong, reactant viscosity can increase, and can suitably add some solvent dioxane.By react complete solution be poured slowly into from
Settle, filter in sub- water, products therefrom is dried into 48h in vacuum drying chamber, be polylactic acid-polyurethane copolymer；
(3) polylactic acid-polyurethane copolymer is immersed into 2V 2vt% acetums and the hydrogenperoxide steam generator of 2V 5wt%
In, it is slowly added to be dissolved in sour (0.5g) solution of piperazinedione of 5ml methanol, after the reaction was complete, with 10wt%NaOH aqueous solutions
Adjusting after pH is in neutrality and filter, washing soaking to trapped substance, filter, and products therefrom is dried 48h in vacuum drying chamber,
As piperazinedione acid polydactyl acid-polyurethane copolymer；(4) the modified poly- breast of piperazinedione acid is added into three-necked flask
Acid-polyurethane copolymer, is warming up to 120 DEG C, and solid is in molten condition, adds 2g mesoporous silica particles, stirs 1h, solid
In molten condition vacuumizing and defoaming, uniformly mixed mixture is poured into mould immediately, mould is put into 100 DEG C of baking oven
2h is heated, rise cures 2h to 120 DEG C again for box temperature degree, demoulds, that is, obtains spherical rubber container.
A8：Polylactic acid-polyurethane copolymer of grafting piperazinedione acid is mixed with polytetrafluoroethylgranule granule, silica dioxide granule
(tetrafluoroethene particle pore size is 2 μm to obtained composition, number-average molecular weight 10000, and silica aperture size is
10nm, 2%) piperazinedione acid grafting rate is
Preparation method is as follows：(1) by 1 mole of 1,4- butanediol (BDO) and 4 moles of hexamethylene diisocyanates (HDI)
It is added in 500ml three-necked flasks, is warming up to 80 DEG C of reaction 5h, after having reacted, is cooled to room temperature, reaction product is transferred to burning
In cup, n-hexane cleaning is added, 5min is stirred with glass bar, is completely dispersed solid product, filter, repeat aforesaid operations three
It is secondary, it is ensured that unreacted hexamethylene diisocyanate has cleaned up in product.By 30 DEG C of vacuum of solid product after cleaning
Dry to constant weight.Dissolved after drying with DMSO stand-by (per 100mL DMSO dissolving 20g HDI-BDO-HDI chain extenders)；
(2) a certain amount of 100ml PEG-600 are added in vacuum reaction bottle, the vaccum dewatering 2h under the conditions of 90 DEG C, water removal
After be cooled to room temperature, then 1mol L- lactides and 1.1mol caprolactones are added into vacuum reaction bottle, add octoate catalyst
Stannous (catalyst quality accounts for the 0.5% of reaction raw materials gross mass), it is after vacuumizing that vacuum reaction bottle is closed, in 140 DEG C of conditions
Lower reaction 24h prepares prepolymer.After the completion of reaction, prepolymer is cooled to 80 DEG C, adds the PEG-600 after 60ml vaccum dewaterings,
After stirring evenly, the DMSO solution of HDI-BDO-HDI chain extenders is added dropwise dropwise.After being added dropwise to complete, 5h is reacted at 80 DEG C.Reacted
Cheng Zhong, reactant viscosity can increase, and can suitably add some solvent dioxane.By react complete solution be poured slowly into from
Settle, filter in sub- water, products therefrom is dried into 48h in vacuum drying chamber, be polylactic acid-polyurethane copolymer；
(3) polylactic acid-polyurethane copolymer is immersed into 2V 2vt% acetums and the hydrogenperoxide steam generator of 2V 5wt%
In, it is slowly added to be dissolved in sour (0.5g) solution of piperazinedione of 5ml methanol, after the reaction was complete, with 10wt%NaOH aqueous solutions
Adjusting after pH is in neutrality and filter, washing soaking to trapped substance, filter, and products therefrom is dried 48h in vacuum drying chamber,
As piperazinedione acid polydactyl acid-polyurethane copolymer；
(4) piperazinedione acid polydactyl acid-polyurethane copolymer is added into three-necked flask, is warming up to 120 DEG C, solid
In molten condition, 1g polytetrafluoroethylgranule granules are added, stir 0.5h, add 1g silica dioxide granules, are stirred for 1h, solid is in molten
Melt state vacuumizing and defoaming, uniformly mixed mixture is poured into mould immediately, mould is put into 100 DEG C of baking oven and is heated
2h, rise cure 2h to 120 DEG C again for box temperature degree, demould, that is, obtain spherical rubber container.
Silica dioxide granule preparation method is the same as A6 steps (1).
A9：It is grafted polylactic acid-polyurethane copolymer expanded PTFE particle, the silica dioxide granule of piperazinedione acid
(varicosity tetrafluoroethene particle pore size is 0.2 μm to mixed obtained composition, number-average molecular weight 10000, silica aperture
Size is 10nm, 2%) piperazinedione acid grafting rate is
Preparation method is as follows：(1) by 1 mole of 1,4- butanediol (BDO) and 4 moles of hexamethylene diisocyanates (HDI)
It is added in 500ml three-necked flasks, is warming up to 80 DEG C of reaction 5h, after having reacted, is cooled to room temperature, reaction product is transferred to burning
In cup, n-hexane cleaning is added, 5min is stirred with glass bar, is completely dispersed solid product, filter, repeat aforesaid operations three
It is secondary, it is ensured that unreacted hexamethylene diisocyanate has cleaned up in product.By 30 DEG C of vacuum of solid product after cleaning
Dry to constant weight.Dissolved after drying with DMSO stand-by (per 100mL DMSO dissolving 20g HDI-BDO-HDI chain extenders)；
(2) a certain amount of 100ml PEG-600 are added in vacuum reaction bottle, the vaccum dewatering 2h under the conditions of 90 DEG C, water removal
After be cooled to room temperature, then 1mol L- lactides and 1.1mol caprolactones are added into vacuum reaction bottle, add octoate catalyst
Stannous (catalyst quality accounts for the 0.5% of reaction raw materials gross mass), it is after vacuumizing that vacuum reaction bottle is closed, in 140 DEG C of conditions
Lower reaction 24h prepares prepolymer.After the completion of reaction, prepolymer is cooled to 80 DEG C, adds the PEG-600 after 60ml vaccum dewaterings,
After stirring evenly, the DMSO solution of HDI-BDO-HDI chain extenders is added dropwise dropwise.After being added dropwise to complete, 5h is reacted at 80 DEG C.Reacted
Cheng Zhong, reactant viscosity can increase, and can suitably add some solvent dioxane.By react complete solution be poured slowly into from
Settle, filter in sub- water, products therefrom is dried into 48h in vacuum drying chamber, be polylactic acid-polyurethane copolymer；
(3) polylactic acid-polyurethane copolymer is immersed into 2V 2vt% acetums and the hydrogenperoxide steam generator of 2V 5wt%
In, it is slowly added to be dissolved in sour (0.5g) solution of piperazinedione of 5ml methanol, after the reaction was complete, with 10wt%NaOH aqueous solutions
Adjusting after pH is in neutrality and filter, washing soaking to trapped substance, filter, and products therefrom is dried 48h in vacuum drying chamber,
As piperazinedione acid polydactyl acid-polyurethane copolymer；
(4) piperazinedione acid polydactyl acid-polyurethane copolymer is added into three-necked flask, is warming up to 120 DEG C, solid
In molten condition, 1g expanded polytetrafluoroethylsealing particles are added, stir 0.5h, 1g silica dioxide granules is added, is stirred for 1h, solid
In molten condition vacuumizing and defoaming, uniformly mixed mixture is poured into mould immediately, mould is put into 100 DEG C of baking oven
2h is heated, rise cures 2h to 120 DEG C again for box temperature degree, demoulds, that is, obtains spherical rubber container.
Silica dioxide granule preparation method is the same as A6 steps (1).
A10：It is grafted the polylactic acid-polyurethane copolymer and expanded PTFE particle, micropore dioxy of piperazinedione acid
(varicosity tetrafluoroethene particle pore size is 0.2 μm to the composition that silicon carbide particle mixes, number-average molecular weight 10000, micropore
Silica aperture size is 1.5nm, 2%) piperazinedione acid grafting rate is
Preparation method is as follows：(1) by 1 mole of 1,4- butanediol (BDO) and 4 moles of hexamethylene diisocyanates (HDI)
It is added in 500ml three-necked flasks, is warming up to 80 DEG C of reaction 5h, after having reacted, is cooled to room temperature, reaction product is transferred to burning
In cup, n-hexane cleaning is added, 5min is stirred with glass bar, is completely dispersed solid product, filter, repeat aforesaid operations three
It is secondary, it is ensured that unreacted hexamethylene diisocyanate has cleaned up in product.By 30 DEG C of vacuum of solid product after cleaning
Dry to constant weight.Dissolved after drying with DMSO stand-by (per 100mL DMSO dissolving 20g HDI-BDO-HDI chain extenders)；
(2) 100ml PEG-600 are added in vacuum reaction bottle, the vaccum dewatering 2h under the conditions of 90 DEG C, cools down after water removal
To room temperature, then 1mol L- lactides and 1.1mol caprolactones are added into vacuum reaction bottle, add octoate catalyst stannous
(catalyst quality accounts for the 0.5% of reaction raw materials gross mass), it is after vacuumizing that vacuum reaction bottle is closed, it is anti-under the conditions of 140 DEG C
24h is answered to prepare prepolymer.Instead, thing is cooled to 80 DEG C under vacuum, adds the PEG-600 after 60ml vaccum dewaterings, stirring
After uniformly, the DMSO solution of HDI-BDO-HDI chain extenders is added dropwise dropwise.After being added dropwise to complete, 5h is reacted at 80 DEG C.Reaction process
In, reactant viscosity can increase, and can suitably add some solvent dioxane.The solution for reacting completion is poured slowly into deionization
Settle, filter in water, products therefrom is dried into 48h in vacuum drying chamber, be polylactic acid-polyurethane copolymer；
(3) polylactic acid-polyurethane copolymer is immersed into 2V 2vt% acetums and the hydrogenperoxide steam generator of 2V 5wt%
In, it is slowly added to be dissolved in sour (0.5g) solution of piperazinedione of 5ml methanol, after the reaction was complete, with 10wt%NaOH aqueous solutions
Adjusting after pH is in neutrality and filter, washing soaking to trapped substance, filter, and products therefrom is dried 48h in vacuum drying chamber,
As piperazinedione acid polydactyl acid-polyurethane copolymer；
(4) piperazinedione acid polydactyl acid-polyurethane copolymer is added into three-necked flask, is warming up to 120 DEG C, solid
In molten condition, 1g expanded polytetrafluoroethylsealing particles are added, stir 0.5h, 1g mesoporous silica particles is added, is stirred for 1h,
Solid is in molten condition vacuumizing and defoaming, immediately pours into mould uniformly mixed mixture, mould is put into 100 DEG C of baking
Heat 2h in case, rise cures 2h to 120 DEG C again for box temperature degree, demoulds, that is, obtains spherical rubber container.
A11：Polylactic acid-polyurethane copolymer is mixed with expanded PTFE particle, mesoporous silica particles
(varicosity tetrafluoroethene particle pore size is 0.2 μm to composition, number-average molecular weight 10000, mesoporous silica pore size
For 1.5nm)
Preparation method is as follows：(1) by 1 mole of 1,4- butanediol (BDO) and 4 moles of hexamethylene diisocyanates (HDI)
It is added in 500ml three-necked flasks, is warming up to 80 DEG C of reaction 5h, after having reacted, is cooled to room temperature, reaction product is transferred to burning
In cup, n-hexane cleaning is added, 5min is stirred with glass bar, is completely dispersed solid product, filter, repeat aforesaid operations three
It is secondary, it is ensured that unreacted hexamethylene diisocyanate has cleaned up in product.By 30 DEG C of vacuum of solid product after cleaning
Dry to constant weight.Dissolved after drying with DMSO stand-by (per 100mL DMSO dissolving 20g HDI-BDO-HDI chain extenders)；
(2) a certain amount of 100ml PEG-600 are added in vacuum reaction bottle, the vaccum dewatering 2h under the conditions of 90 DEG C, water removal
After be cooled to room temperature, then 1mol L- lactides and 1.1mol caprolactones are added into vacuum reaction bottle, add octoate catalyst
Stannous (catalyst quality accounts for the 0.5% of reaction raw materials gross mass), it is after vacuumizing that vacuum reaction bottle is closed, in 140 DEG C of conditions
Lower reaction 24h prepares prepolymer.After the completion of reaction, prepolymer is cooled to 80 DEG C, adds the PEG-600 after 60ml vaccum dewaterings,
After stirring evenly, the DMSO solution of HDI-BDO-HDI chain extenders is added dropwise dropwise.After being added dropwise to complete, 5h is reacted at 80 DEG C.Reacted
Cheng Zhong, reactant viscosity can increase, and can suitably add some solvent dioxane.By react complete solution be poured slowly into from
Settle, filter in sub- water, products therefrom is dried into 48h in vacuum drying chamber, be polylactic acid-polyurethane copolymer；
(3) polylactic acid-polyurethane copolymer is added into three-necked flask, is warming up to 120 DEG C, solid is in molten condition, is added
Enter 1g expanded polytetrafluoroethylsealing particles, stir 0.5h, add 1g mesoporous silica particles, be stirred for 1h, solid is in molten
State vacuumizing and defoaming, uniformly mixed mixture is poured into mould, mould is put into 100 DEG C of baking oven and heats 2h immediately,
Rise cures 2h to 120 DEG C again for box temperature degree, demoulds, that is, obtains spherical rubber container.
A12：It is grafted the polylactic acid-polyurethane copolymer and expanded PTFE particle, micropore dioxy of piperazinedione acid
(varicosity tetrafluoroethene particle pore size is 0.2 μm to the composition that silicon carbide particle mixes, number-average molecular weight 10000, micropore
Silica aperture size is 1nm, 3%) piperazinedione acid grafting rate is
Preparation method is as follows：(1) by 1 mole of 1,4- butanediol (BDO) and 4 moles of hexamethylene diisocyanates (HDI)
It is added in 500ml three-necked flasks, is warming up to 80 DEG C of reaction 5h, after having reacted, is cooled to room temperature, reaction product is transferred to burning
In cup, n-hexane cleaning is added, 5min is stirred with glass bar, is completely dispersed solid product, filter, repeat aforesaid operations three
It is secondary, it is ensured that unreacted hexamethylene diisocyanate has cleaned up in product.By 30 DEG C of vacuum of solid product after cleaning
Dry to constant weight.Dissolved after drying with DMSO stand-by (per 100mL DMSO dissolving 20g HDI-BDO-HDI chain extenders)；
(2) a certain amount of 100ml PEG-600 are added in vacuum reaction bottle, the vaccum dewatering 2h under the conditions of 90 DEG C, water removal
After be cooled to room temperature, then 1mol L- lactides and 1.1mol caprolactones are added into vacuum reaction bottle, add octoate catalyst
Stannous (catalyst quality accounts for the 0.5% of reaction raw materials gross mass), it is after vacuumizing that vacuum reaction bottle is closed, in 140 DEG C of conditions
Lower reaction 24h prepares prepolymer.After the completion of reaction, prepolymer is cooled to 80 DEG C, adds the PEG-600 after 60ml vaccum dewaterings,
After stirring evenly, the DMSO solution of HDI-BDO-HDI chain extenders is added dropwise dropwise.After being added dropwise to complete, 5h is reacted at 80 DEG C.Reacted
Cheng Zhong, reactant viscosity can increase, and can suitably add some solvent dioxane.By react complete solution be poured slowly into from
Settle, filter in sub- water, products therefrom is dried into 48h in vacuum drying chamber, be polylactic acid-polyurethane copolymer；
(3) polylactic acid-polyurethane copolymer is immersed into 2V 2vt% acetums and the hydrogenperoxide steam generator of 2V 5wt%
In, it is slowly added to be dissolved in sour (0.8g) solution of piperazinedione of 5ml methanol, after the reaction was complete, with 10wt%NaOH aqueous solutions
Adjusting after pH is in neutrality and filter, washing soaking to trapped substance, filter, and products therefrom is dried 48h in vacuum drying chamber,
As piperazinedione acid polydactyl acid-polyurethane copolymer；
(4) piperazinedione acid polydactyl acid-polyurethane copolymer is added into three-necked flask, is warming up to 120 DEG C, solid
In molten condition, 1g expanded polytetrafluoroethylsealing particles are added, stir 0.5h, 1g mesoporous silica particles is added, is stirred for 1h,
Solid is in molten condition vacuumizing and defoaming, immediately pours into mould uniformly mixed mixture, mould is put into 100 DEG C of baking
Heat 2h in case, rise cures 2h to 120 DEG C again for box temperature degree, demoulds, that is, obtains spherical rubber container.
A13：Polylactic acid
Preparation method is as follows：(1) 100ml PEG-600 are added in vacuum reaction bottle, the vaccum dewatering under the conditions of 90 DEG C
2h, is cooled to room temperature after water removal, then 1mol L- lactides and 1.1mol caprolactones are added into vacuum reaction bottle, adds and urges
Agent stannous octoate (catalyst quality accounts for the 0.5% of reaction raw materials gross mass), it is after vacuumizing that vacuum reaction bottle is closed,
24h is reacted under the conditions of 140 DEG C and prepares prepolymer.
(2) polylactic acid prepolymer is added into three-necked flask, is warming up to 120 DEG C, solid is in molten condition, and solid is in melting
State vacuumizing and defoaming, uniformly mixed mixture is poured into mould, mould is put into 100 DEG C of baking oven and is heated immediately
2h, rise cure 2h to 120 DEG C again for box temperature degree, demould, that is, obtain spherical rubber container.
A14:Composition (the varicosity four that polylactic acid is mixed with expanded PTFE particle, mesoporous silica particles
Vinyl fluoride particle pore size is 0.2 μm, and number-average molecular weight 10000, mesoporous silica pore size is 1nm)
Preparation method is as follows：(1) 100ml PEG-600 are added in vacuum reaction bottle, the vaccum dewatering under the conditions of 90 DEG C
2h, is cooled to room temperature after water removal, then 1mol L- lactides and 1.1mol caprolactones are added into vacuum reaction bottle, adds and urges
Agent stannous octoate (catalyst quality accounts for the 0.5% of reaction raw materials gross mass), it is after vacuumizing that vacuum reaction bottle is closed,
24h is reacted under the conditions of 140 DEG C and prepares prepolymer.
(2) polylactic acid performed polymer is added into three-necked flask, is warming up to 120 DEG C, solid is in molten condition, and it is puffing to add 1g
Polytetrafluoroethylgranule granule, stirs 0.5h, adds 1g mesoporous silica particles, is stirred for 1h, solid is vacuumized in molten condition
Deaeration, uniformly mixed mixture is poured into mould, mould is put into 100 DEG C of baking oven and heats 2h immediately, and rise supplies case
Temperature cures 2h to 120 DEG C again, demoulds, that is, obtains spherical rubber container.
B1:Band
C1:Band stopple
In embodiment, when carrying out packaging rose, water is stored in modified polyurethane composition.
Embodiment 1
Combined by A3, B1, C1, obtain combination container, pack rose.
Embodiment 2
Combined by A4, B1, C1, obtain combination container, pack rose.
Embodiment 3
Combined by A5, B1, C1, obtain combination container, pack rose.
Embodiment 4
Combined by A6, B1, C1, obtain combination container, pack rose.
Embodiment 5
Combined by A7, B1, C1, obtain combination container, pack rose.
Embodiment 6
Combined by A8, B1, C1, obtain combination container, pack rose.
Embodiment 7
Combined by A9, B1, C1, obtain combination container, pack rose.
Embodiment 8
Combined by A10, B1, C1, obtain combination container, pack rose.
Embodiment 9
Combined by A11, B1, C1, obtain combination container, pack rose.
Embodiment 10
Combined by A12, B1, C1, obtain combination container, pack rose.
Comparative example 1
Combined by A1, B1, C1, obtain combination container, pack rose.
Comparative example 2
Combined by A2, B1, C1, obtain combination container, pack rose.
Comparative example 3
Combined by A13, B1, C1, obtain combination container, pack rose.
Comparative example 4
Combined by A14, B1, C1, obtain combination container, pack rose.
Comparative example 5
Combined by B1, C1, pack rose.
The rose packed to above-described embodiment 1~10 and comparative example 1~5 and modified polyurethane composition A are into traveling
Row test, test method are as follows：
1st, fresh keeping time：Room temperature is at 18 degree or so, air humidity 90%, the combination container bag prepared with above-described embodiment
Dress, observes the service life of rose；
2nd, bacteriostasis rate：Dipping culture rule is that sample is immersed in bacteria suspension, after cultivating a period of time, by flat
The method that plate counts carries out count plate, and then calculates antibiotic rate, antibiotic rate=(bacterium number-antimicrobial sample on blank sample
On bacterium number) bacterium number × 100% on/blank sample；
3rd, degrade：A samples (1.0cm × 1.0cm, about 0.25g) prepared by multiple embodiments of precise are thrown respectively
It is molten into the borax buffering equipped with 50mL normal saline solutions, the acetic acid of 50mL pH=4, sodium acetate buffer and pH=9.18
In the beaker of liquid, sealing, and be placed in 37 DEG C of biochemical cultivation case and carry out degradation experiment, observe sample broke institute's used time
Between.
1 the performance test results of table
In summary, it is known that, modified polyurethane composition and spherical polyurethane, spherical poly- breast in flower arrangement device of the invention
Acid, be not grafted piperazinedione acid, blending polytetrafluoroethylgranule granule and silica dioxide granule contrasted, flower arrangement device of the invention
There is very big advantage in terms of fresh flower packaging, fresh-keeping, transport, environmental protection.
Above-mentioned example is merely illustrative, some features of the feature for explaining the present invention.Appended claim
It is intended to require the scope as wide as possible being contemplated that, and embodiments as presented herein is only according to all possible embodiment
Combination selection embodiment explanation.Therefore, the purpose of applicant is appended claim not by the explanation present invention
Feature exemplary selectional restriction, and the progress in science and technology will not formed due to the inaccuracy of language performance and not
The possible equivalent or son being presently considered are replaced, and these changes should also be interpreted by appended in the conceived case
Claim covers.
Claims (7)
1. one kind flower arrangement device, it is characterised in that it is made of the spherical rubber container of band neck, band stopple and band, the band
Stopple fills in the band spherical rubber container neck interior of neck, and is sleeved on by band outside the spherical rubber container neck of band neck admittedly
Fixed, the band stopple top is flushed with the spherical rubber container neck top of neck；The spherical rubber container material of band neck
For modified polyurethane composition, band material is rubber, and band stopple material is EVA foams or high-elastic PE, wherein, the modification gathers
Urethane composition by polylactic acid-polyurethane copolymer be grafted piperazinedione acid, then with expanded PTFE, micropore dioxy
SiClx is blended to obtain.
2. device of arranging flowers according to claim 1, it is characterised in that piperazinedione on the polylactic acid-polyurethane copolymer
The grafting rate of acid is 1~3%.
3. device of arranging flowers according to claim 2, it is characterised in that piperazinedione on the polylactic acid-polyurethane copolymer
The grafting rate of acid is 1~2%.
4. device of arranging flowers according to claim 1, it is characterised in that the top bore with the spherical rubber container of neck is
1.5~3cm, the distance at top and spherical upper end is 2~3cm.
5. device of arranging flowers according to claim 1, it is characterised in that the width of the band is 2~3cm.
6. device of arranging flowers according to claim 1, it is characterised in that a diameter of 5~8cm with stopple, thickness for 1~
2cm, 0.05~0.08cm of aperture.
7. according to any one of the claim 1~6 flower arrangement device, it is characterised in that the flower arrangement device is applied to flowers
Packaging, fresh-keeping, storage and transport.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE156466C (en) * | ||||
| FR2732548A1 (en) * | 1995-04-07 | 1996-10-11 | Rousseau Pierre | Sealed container for temporary storage of cut flowers |
| CN2389782Y (en) * | 1999-05-20 | 2000-08-02 | 何金焕 | Moisture retaining and ventilating adjusting packaging paper |
| CN202156668U (en) * | 2011-06-22 | 2012-03-07 | 攀枝花学院 | Flower bunch sleeve |
| CN103404423A (en) * | 2013-08-23 | 2013-11-27 | 北京化工大学 | Wall-mounted flower freshness protection package |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04126018A (en) * | 1990-09-16 | 1992-04-27 | Hanadai:Kk | Partial wrapping of flowers and wrapping tool therefor |
-
2016
- 2016-08-31 CN CN201610791803.2A patent/CN106395162B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE156466C (en) * | ||||
| FR2732548A1 (en) * | 1995-04-07 | 1996-10-11 | Rousseau Pierre | Sealed container for temporary storage of cut flowers |
| CN2389782Y (en) * | 1999-05-20 | 2000-08-02 | 何金焕 | Moisture retaining and ventilating adjusting packaging paper |
| CN202156668U (en) * | 2011-06-22 | 2012-03-07 | 攀枝花学院 | Flower bunch sleeve |
| CN103404423A (en) * | 2013-08-23 | 2013-11-27 | 北京化工大学 | Wall-mounted flower freshness protection package |
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Denomination of invention: A flower arrangement device Granted publication date: 20180515 Pledgee: Kunming Dongfeng Sub branch of Bank of China Ltd. Pledgor: SHANGHAI FENSHANG NETWORK TECHNOLOGY Co.,Ltd. Registration number: Y2024110000078 |