CN106395162A

CN106395162A - Flower arrangement device

Info

Publication number: CN106395162A
Application number: CN201610791803.2A
Authority: CN
Inventors: 王柯
Original assignee: Shanghai Fenshang Network Technology Co Ltd
Current assignee: Shanghai Fenshang Network Technology Co Ltd
Priority date: 2016-08-31
Filing date: 2016-08-31
Publication date: 2017-02-15
Anticipated expiration: 2036-08-31
Also published as: CN106395162B

Abstract

The invention provides a flower arrangement device. The flower arrangement device consists of a neck-provided spherical rubber container, a lace hole plug and a tying lace; the lace hole plug is inserted into the neck part of the neck-provided spherical rubber container and fixedly sleeves the outer part of the neck part of the neck-provided spherical rubber container through the tying lace; the top end of the lace hole plug is aligned to the top end of the neck-provided spherical rubber container. The flower arrangement device disclosed by the invention has quite great advantages in fresh flower packaging, preservation, transportation and environmental protection.

Description

A kind of flower arrangement device

Technical field

The invention belongs to a kind of flower arrangement device, more particularly it relates to flower arrangement device composition material and application.

Background technology

A kind of flower is that timeliness and seasonality be very strong and growth conditionss have certain requirements plant.The wilderness demand of flower It is the symbol of social progress and human civilization, be people's living standard quality and the important symbol appreciating temperament and interest raising, be deeply subject to big Many likes.

Flower packaging is one of logistics important elements, and it is the terminal producing, and the starting point of logistics is storing, transports, selling on a commission basis During there is defencive function, quantitative function, blip facility, main purpose protect its use value, with anti-pollution or rotten Rotten, in order to have higher quality when flower is sold.

At present, the flower manner of packing adopting in flower shop is usually after the colored material first client chosen prepares, then uses Color packing paper is wrapped from the outside, finally with colored ribbon, wrapping paper and flower is bundled into bouquet.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, larger, the above-mentioned packaging side of the sales volume ratio of flower Formula can be delayed client and take colored demand in the very first time.

The packaging phenomenon of " squash type " of flower is more universal, and the quality of flowers product cannot be guaranteed." squash type " Flower is packed, and every goods can save the cost of transportation of dozens of yuan, but flower reaches quality degradation when in client's handss, flower The proportion of goods damageds up to more than 20%.

Flower is the fresh and alive plant of sight, and the follow-up supervention of harvesting is educated, Growth and anthesis, is by the life entity breathing, so The fresh-keeping particular importance that also seems of flower.

In addition, if the packaging material of flower can reclaim or be degradable, to resource using and the protection of environment have Certain effect.

For the problems referred to above, now need a kind of flower arrangement device badly, this combination container packs in flower, fresh-keeping, transport, environmental protection Aspect has very big advantage.

Content of the invention

In order to solve the above problems, one aspect of the present invention provides a kind of flower arrangement device, described flower arrangement device band cervical region Spherical rubber container, band stopple and band composition, described band stopple fills in band cervical region spherical rubber container neck interior, and passes through Band is enclosed within band cervical region spherical rubber container cervical region external stability, described band stopple top and band cervical region spherical rubber container cervical region Top flushes.

In one embodiment, described band cervical region spherical rubber container material is modified polyurethane composition, band material Expect for rubber, carry stopple material to be EVA foam or high-elastic PE, wherein, modified polyurethane composition includes at least polylactic acid, poly- ammonia Ester, piperazinedione acid and expanded PTFE.

In one embodiment, described modified polyurethane composition also comprises mesoporous silica.

In one embodiment, described modified polyurethane composition is by grafting piperazine on polylactic acid-polyurethane copolymer Two keto acids, are then obtained with expanded PTFE, mesoporous silica blending.

In one embodiment, on described polylactic acid-polyurethane copolymer, the percent grafting of piperazinedione acid is 1～3%.

In one embodiment, on described polylactic acid-polyurethane copolymer, the percent grafting of piperazinedione acid is 1～2%.

In one embodiment, the described top bore with the spherical rubber container of cervical region is 1.5～3cm, top and ball The distance of shape upper end is 2～3cm.

In one embodiment, the width of described band is 2～3cm.

In one embodiment, described a diameter of 5～8cm with stopple, thickness is 1～2cm, aperture 0.05～ 0.08cm.

Flower arrangement device described in another aspect of the present invention is applied to packaging, fresh-keeping, storage and the transport of flowers.

It is more readily understood the above-mentioned of the application and other features, aspect and advantage with reference to described further below.

Brief description

Fig. 1：The band spherical rubber container of cervical region

Fig. 2：Band

Fig. 3：Band stopple

Fig. 4：Flower arrangement device (1, band the spherical rubber container of cervical region；2nd, band；3rd, consent with holes, 4, band stopple)

Specific embodiment

The embodiment of the participation in the election detailed description being preferable to carry out method of the invention below and inclusion can be more easily understood this Bright content.Unless otherwise defined, all technology used herein and scientific terminology have common with art of the present invention The identical implication that technical staff is generally understood that.When there is contradiction, the definition in this specification is defined.

As used herein term " by ... preparation " synonymous with "comprising".Term "comprising" used herein, " inclusion ", " having ", " containing " or its any other deformation it is intended that cover non-exclusionism inclusion.For example, comprise the combination of listed elements Thing, step, method, product or device are not necessarily solely those key elements, but can include not expressly listed other key elements or This kind of compositionss, 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 so as to not comprise the material in addition to the material that those describe, but relative normal Except rule impurity.When phrase " Consists of " occurs in and is rather than immediately following after theme in the clause of claim main body, It is only limited to the key element described in this clause；Other key elements are not excluded outside as overall described claim.

Equivalent, concentration or other value or parameter are excellent with scope, preferred scope or a series of upper limit preferred value and lower limit During the Range Representation that choosing value limits, this is appreciated that and specifically discloses by any range limit or preferred value and any scope All scopes that arbitrary pairing of lower limit or preferred value is formed, regardless of whether whether this 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 numerical range is herein described, unless otherwise indicated, otherwise this scope is intended to include its end Value and all integers within the range and fraction.

Singulative includes plural number and object is discussed, unless the context clearly dictates otherwise." optional " or " arbitrarily A kind of " refer to that the item describing thereafter or event may or may not occur, and this description include event generation situation and The situation that event does not occur.

Approximate term in specification and claims is used for modifying quantity, represents that the present invention is not limited to this concrete Quantity, also includes the part of the correction of acceptable change without lead to related basic function close to this quantity.Phase Answer, modify a numerical value with " about ", " about " etc., mean and the invention is not restricted to this exact numerical.In some examples, approximately Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, scope limits permissible Combination and/or exchange, these scopes include all subranges contained therebetween if not stated otherwise.

Additionally, the quantitative requirement to key element or component for the indefinite article " a kind of " and " one " before key element of the present invention or component (i.e. occurrence number) unrestriction.Therefore " one " or " a kind of " should be read as including one or at least one, and odd number The key element of form or component also include plural form, unless the obvious purport of described quantity refers to singulative.

" polymer " means by the polymerizable compound prepared by the monomer of the identical or different type of polymerization.Generic term " polymer " comprises term " homopolymer ", " copolymer ", " terpolymer " and " copolymer ".

" copolymer " means the polymer by being polymerized at least two different monomers preparations.Generic term " copolymer " includes (it is general with term " terpolymer " for term " copolymer " (it is typically in order to refer to by the polymer of two kinds of different monomers preparations) In order to refer to by the polymer of three kinds of different monomers preparations).It also comprises the polymer manufacturing by being polymerized more kinds of monomers. " blend " means the polymer that two or more polymer is formed by the common mixing of physics or chemistry method.

One aspect of the present invention provides a kind of flower arrangement device, the spherical rubber container of described flower arrangement device band cervical region, with holes Plug and band composition, described band stopple fills in band cervical region spherical rubber container neck interior, and is enclosed within band cervical region ball by band Shape rubber container cervical region external stability, described band stopple top is flushed with band cervical region spherical rubber container cervical region top.

Polyurethane (Polyurethane, PU) has the carbamate (- NHCOO-) unit of repetition, except containing substantial amounts of Outside carbamate groups, may be also containing hydrogen bond between ester group, ether, urea groups and macromole etc. in structure.PU generally by Polyhydric alcohol (PEPA or polyether polyol), diisocyanate and chain extender polycondensation synthesis, can be divided into soft in its structure Section and hard section two parts, soft section is made up of polyester or/and polyethers, and hard section is to become packet by epoxide formic acid esters, chain extender etc. Become, can be seen that PU is a kind of linear block polymer by this version, the formation of soft section and hard section and its respective heat Mechanics incompatibility is related, and due to there are different thermodynamics incompatibilities, the formation that flocks together of the soft section in polymer is soft Duan Xiang, hard section flocks together again and forms hard section phase, and microphase-separated occurs then.Separated degree between soft, hard section is passed through hard Oxygen key amount between section and hard section can be seen that, and soft, hard section phase mixability can be by the oxygen key amount between hard section and soft section Find out.The hard section of polyurethane mutually serves the effect of physical crosslinking in the base, and soft section is crosslinked by hard section phase region, is polyurethane Pliability provides necessary condition, just because of the unique micro phase separation structure of polyurethane so that its have excellent elasticity, The advantages of 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 polymerized with lactic acid (LA) for principal monomer Polymer, the raw material of lactic acid is starch, by the plants such as Semen Maydiss, Semen Tritici aestivi extract, starch through enzyme decompose after obtained Portugal Grape sugar, recycles the role transformation of lactic acid bacteria fermentation to become PLA, is a kind of tunning of microorganism.It can be seen that this raw material Rich and easy to get, and renewable, substantially reduce the dependence to petrochemical industry, be conducive to environmental conservation.According to optically active not With lactic acid can be divided into D-lactic acid and L-lactic acid, and the raceme being made up of equivalent d-isomer and levo form) lactic acid, phase Ying Di, polylactic acid also has these three basic stereoisomers of poly- L-lactic acid, Poly-L-lactic acid and ploy DL lactic caid, a wherein poly- left side Rotation lactic acid and ploy DL lactic caid are easier to obtain.

PLA is a kind of typical biodegradable aliphatic polyester, and the final product of its degraded is pollution-free, non-hazardous H₂O and CO₂, various products use convenient post-treatment, environmental protection, there is nontoxic, nonirritant, also there is certain biocompatibility, It is widely applied to biomedicine field.The mechanical performance of polylactic acid is good with physical property, antibacterial and mouldproof, and plasticization is processed into Type, all has wide market prospect in all many-sides such as industrial and civilian plastics, packaging, hygienic article, fabric.

PLA is a kind of aliphatic polyester, contains ester bond in molecular structure, facile hydrolysiss so as to 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 degraded, principle For the ester bond in water molecules attack PLA strand, ester bond is in H⁺Effect is lower to rupture, and macromolecular chain disconnects, and is degraded to water soluble Lactic acid monomer, and then be decomposed into carboxylic acid (end carboxyl) and alcohol, the catabolite containing end carboxyl is typically trapped in PLA product Portion, can be produced from acceleration effect, so it has been generally acknowledged that the inside degradation rate of PLA product has research table more than superficial degradation speed 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 topmost degradation material in nature, the enzyme in nature can not direct attack PLA, but first allow PLA There is hydrolysis so as to strand rupture, molecular weight reduction, subsequently accept the attack of enzyme, degrade further.Water-fast polymerization The process that thing is changed into water-soluble substanceses in vivo is referred to as molten candle effect.Macroscopically see, corrosion process shows as the structure quilt of sample Destroy, volume diminishes, and is broken into fragment, lose original mechanical strength, overall structure modification is weightless, finally degradable and quilt Absorption of human body or exclusion are external；See on microcosmic that, as polymer macromolecule chain break, molecular weight reduces rapidly, becomes small molecule And be dissolved in body fluid, gulped down by cell instigate and convert, the degraded of metabolism PLA shows as procedure below:After a large amount of water suctions in PLA molecule, Cause the ester linkage breaking in macromolecular chain, hydrolyze, then solable matter constantly spreads, PLA sample burst produces fragment, Subsequently fragment dissolves in time.

The soft section of modified polyurethane is made up of biodegradable aliphatic polyesters such as polylactic acid, polycaprolactones, hard section then by Aliphatic (as isophorone diisocyanate) or alicyclic diisocyanate and small molecule glycol composition, thus obtain degradable , avirulent polyurethane.Ester due to this kind of polyurethane soft section is typically synthesized with small-molecule substance, and is easy to water Solution, can also become small molecule after hydrolysis.

The basic structure of diketopiperazine compound is by the Cyclic dipeptides of 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 biological activity and Pharmacologically active, becomes an important pharmacophore in pharmaceutical chemistry.A series of rings two are found in recent years from Marine microorganism Peptides, research shows that its function is not limited to the aspects such as antibacterial, cytotoxic activity, in quorum sensing regulatory mechanism Act as the key player of signaling molecule.

Piperazine ring is conventional aza ring in pharmaceutical chemistry research, and introducing piperazine ring in drug molecule can effectively adjust The physicochemical property of nodal compound, improves the pharmacokinetic property of medicine, and a lot of compounds containing piperazine ring show strong Antifungal activity, a series of derivants that chain amino piperazine ring is modified show good antifungic action, show wide resisting Funguses are composed, and have good inhibition to antibacterials such as bacillus subtilises.

In the present invention, piperazinedione acid has to bacillus subtilis, Pseudomonas fluorescence and staphylococcus aureuses etc. Certain inhibitory action, can extend the fresh keeping time of flower.

Expanded PTFE (expanded Polytetrafluoroethylene, abbreviation e-PTFE) is a kind of new The macromolecular material of environmental protection, is widely used in the fields such as clothing, building, electronics, chemical industry medical treatment.It is by politef (PTFE) it is prepared from through stretch processes, defines the duct of about 0.1～1.5 μm of rank, porosity is up to 82%.e- PTFE inherits the advantage of PTFE, has the microcosmic network structure of " microfibre node ", extremely excellent resistance to chemical corrosion, Ageing resistace, low-surface-energy, insulating properties and fire resistance.The micron level duct that it has, can effectively stop liquid Passing through of state water and solid dust, has excellent functions of waterproof and dustproof, and high voidage can allow air and water vapour divide again Son passes through, and has good water proof and dust proof and air-moisture-permeable function, and therefore e-PTFE is forth generation the most promising Waterproof and breathable product.

Mesoporous silica is with Organic substance as template, is synthesized by the interfacial assembly between template and inorganic species Have narrow pore size distribution, pore passage structure rule inorganic porous material.

Compared with traditional porous material, being mainly characterized by of orderly poromerics:

L () has well-regulated pore passage structure；

(2) pore-size distribution is very narrow, and can adjust between 1.3 1 2nm；

(3) through optimum synthesis condition or post processing, can have good heat stability and hydrothermal stability；

(4) granule has well-regulated profile；

(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：

C by 2mol_2-8-2Surfactant and 10mol Na₂SiO₃·9H₂O, is dissolved in the deionized water of 30.0ml respectively In, in the case of being then stirred at room temperature, two kinds of solution are mixed rapidly, after 20 minutes, dropwise instill in the case of stirring The sulfuric acid solution of 3mol/L, reconciling PH is between 9-10, stands 5h, then constant temperature 3 in 80 DEG C of baking oven under mixed liquor room temperature My god, the solid precipitation obtaining, through filtering, dries 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, and constant temperature 6h obtains the product of roasting.

The sign of mesoporous silica：

Using Barertt-Joyner-Halenda (BJH) model analysiss aperture, synthesis sample aperture 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 mouth flask, it is warming up to 80 DEG C of reaction 5h, after having reacted, is cooled to room temperature, product is transferred in beaker, add just own Alkane cleans, and stirs 5min with Glass rod, so that solid product is completely dispersed, sucking filtration, repeats aforesaid operations three times it is ensured that in product Unreacted hexamethylene diisocyanate cleans up.30 DEG C of solid product after cleaning is dried under vacuum to constant weight.Dry Stand-by with DMSO dissolving (every 100mL DMSO dissolves 20g HDI-BDO-HDI chain extender) after dry；

(2) 100ml PEG-600 is added in vacuum response bottle, vaccum dewatering 2h under the conditions of 90 DEG C, lowers the temperature after eliminating water To room temperature, then add 1mol L- lactide and 1.1mol caprolactone in vacuum response bottle, add octoate catalyst stannous (catalyst quality accounts for the 0.5% of reaction raw materials gross mass), will be airtight for vacuum response bottle after evacuation, 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 dewatering, stirring After uniformly, the dropwise DMSO solution of Deca HDI-BDO-HDI chain extender.After being added dropwise to complete, react 5h at 80 DEG C.Course of reaction In, reactant viscosity can increase, and can suitably add some solvent dioxane.The solution that reaction is completed is poured slowly into deionization Settle in water, sucking filtration, products therefrom is dried in vacuum drying oven 48h, as polylactic acid-polyurethane copolymer；

(3) polylactic acid-polyurethane copolymer is immersed the hydrogenperoxide steam generator of 2V 2vt% acetum and 2V 5wt% In, it is slowly added to be dissolved in piperazinedione acid (0.5g) solution of 5ml methanol, after reaction completely, use 10wt%NaOH aqueous solution Adjust pH be in neutrality after filter, soaking to trapped substance, washing, sucking filtration, products therefrom is dried 48h in vacuum drying oven, It is piperazinedione acid polydactyl acid-polyurethane copolymer；

(4) add piperazinedione acid polydactyl acid-polyurethane copolymer in there-necked flask, be warming up to 120 DEG C, solid In molten condition, add 1g expanded polytetrafluoroethylsealing granule, stir 0.5h, add 1g mesoporous silica particles, be stirred for 1h, Solid is in molten condition vacuumizing and defoaming, pours the mixture of mix homogeneously in mould into immediately, mould is put into 100 DEG C of baking Heat 2h in case, raise for case temperature to 120 DEG C of recurring 2h, the demoulding, that is, obtain spherical rubber container.

Observe the size in modified polyurethane aperture by SEM, find modified polyurethane composition aperture in 0.3～0.4nm.

The micron level duct that expanded PTFE and mesoporous silica have, can effectively stop aqueous water and solid Passing through of body dust, has excellent functions of waterproof and dustproof, and high voidage can allow air and water vapour molecule smoothly lead to again Cross, there is good airing function, both synergism, improve the size in modified polyurethane aperture, improve modified polyurethane The waterproof and breathable function of compositionss.

The aperture of air-vent is more than 0.33nm, and less than 0.4nm, that is, the aperture of air-vent is more than oxygen molecule and carbon dioxide The diameter of molecule, less than hydrone diameter so that oxygen and carbon dioxide molecule can pass through, hydrone cannot pass through, from And realize air permeable waterproof.

In one embodiment, the number-average molecular weight of described expanded PTFE is 5000～30000；Preferably, The number-average molecular weight of described expanded PTFE is 8000～20000.

Number-average molecular weight is to be measured based on membrane permeation method.

Membrane osmotic pressure method adopts two capillaries, two infiltration connection ponds, the device that centre semipermeable membrane AB separates, infiltration While containing macromolecular solution, another side contains solvent in pond.The pore size of semipermeable membrane allows solvent molecule freely to pass through, and solute divides Sub-volume is big, can not pass through semipermeable membrane.When infiltration starts, solvent molecule is more than solution by the quantity that semipermeable membrane enters solution pool In pond, solvent molecule enters the quantity of solvent cell by semipermeable membrane.Solution concentration is gradually diluted, the capillary tube of solution pool Liquid level gradually rises, and when system reaches thermodynamic equilibrium class hour, solution pool reaches certain value with the capillary tube liquid-column height difference of solvent cell, The two pond solvent molecules quantity that interpenetrates reaches dynamic equilibrium, the at this moment difference of two capillary liquid-column heights, i.e. the pressure of solvent post Power difference is the osmotic pressure π of solution.

π=△ h D (1)

In formula:△ h is the difference (cm) of capillary tube liquid-column height；D is the density (g/mL) of solvent.The infiltration of perfect solution Pressure Van't Hoff (Vant Hoff) two laws are represented by:

π=NRT/V=RTC/Mn (2)

In formula：V liquor capacity, molal quantity in V for the N solute, the number-average molecular weight of Mn solute, C solution Concentration (g/100mL), R constant, 848.4；T operates absolute temperature.

By (1), (2) formula obtains Δ h D=RTC/Mn

Mn=RT/ [(Δ h/c) D]

Δ h is that Δ h c claim reduced osmotic pressure from the Δ h value numerically read.

Van't Hoff's law, only in perfect solution, could be set up in the solution of infinite dilution, that is,:

Mn=RT/ (Δ h/c) c=0 D (3)

So (Δ h/c) c=0 is tried to achieve using extrapolation, that is, prepare a series of macromolecule polymer solution of variable concentrations, Measure its Δ h value respectively, then with concentration c as abscissa, with Δ h/c as vertical coordinate, draw a straight line this 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, in the external force effect of very little Lower energy produces compared with large deformation, removes 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 subject to external force When effect deforms, there is the ability of rapid recovery, 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 foam, antistatic foam, conducting foam, EPE, antistatic EPE, PORON, CR, EVA, bridge formation PE, SBR, EPDM etc., have easy to use, bending freely, a series of features such as the ultra-thin, dependable performance of volume.

Foam has following feature：(1) the extraordinary shield effectiveness of low-pressure, shield effectiveness is more than 90dB；(2) there is bullet Property, lightweight.(3) anticorrosion nickel coating can cathodic protection；(4) low surface contacted resistance；(5) quickly pressure-sensitive fixation；(6) Client may specify length；(7) numerous section selection；(8) UL level fire prevention.

Foam product with stable quality, resistance to hot pressing, difficult for drop-off, tension intensity is high, after product installation, through -20 DEG C of low temperature To 80 DEG C of high temperature, loop cycle test still keeps this quality in 72 hours.Have 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 Comparing, EVA is due to introducing VAM in strand, thus reducing high-crystallinity, improve pliability, anti-impact Hitting property, filler intermiscibility and heat seal performance, are widely used in foaming shoe material, functional greenhouse film, packaging film, PUR, electricity The field such as line cable and toy.

EVA product of rubber and plastic is novel environment friendly plastics expanded material, has good buffering, antidetonation, heat-insulated, moistureproof, anti-ization Learn corrosion the advantages of, and nontoxic, do not absorb water.

In one embodiment, the width of described band is 2～3cm.

In the present invention, modified polyurethane composition includes at least polylactic acid, polyurethane, piperazinedione acid and e-PTFE Ethylene, mesoporous silica；By polylactic acid, piperazinedione acid modified polyurethane, then with expanded PTFE and micropore Silica dioxide granule carries out function that the modified polyurethane composition that prepare have environmental protection, waterproof and breathable and sterilization is blended, Ensure that the plants such as flowers pluck 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, it has good degradation property, Final catabolite is H₂O and CO₂, to environment non-hazardous, therefore modified polyurethane composition not only has excellent elasticity, draws The advantages of stretching performance, wearability and low clean crystalline substance and spend, and structure is easy to process and design, and efficient and convenient during packaging flower, it is breathed freely Waterproof, antibacterial effective efficiency help the plants such as flowers during flower transport and storage and educate, grow in the follow-up supervention of harvesting Bloom, and, when modified polyurethane composition breakage can not reuse, it is degradable, will not be to environment.

Below by embodiment, the present invention is specifically described.Be necessary it is pointed out here that, following examples 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 improvement made according to the content of the invention described above and adjustment, still fall within protection scope of the present invention.

In addition, if not having other explanations, raw materials used is all commercially available, is purchased from traditional Chinese medicines chemical reagent.

A1：Polyurethane

Preparation method is as follows：(1) by 1 mole of BDO (BDO) and 4 moles of hexamethylene diisocyanates (HDI), It is added in 500ml there-necked flask, be warming up to 80 DEG C of reaction 5h, after having reacted, be cooled to room temperature, product is transferred to burning In cup, add normal hexane cleaning, stir 5min with Glass rod, so that solid product is completely dispersed, sucking filtration, repeats aforesaid operations three Secondary it is ensured that in product unreacted hexamethylene diisocyanate clean up.By the 30 DEG C of vacuum of solid product after cleaning It is dried to constant weight, obtain base polyurethane prepolymer for use as；

(2) triethylene glycol (triethylene glycol is 3% with the mass ratio of performed polymer) is added in above-mentioned performed polymer, is 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 mix immediately all Even mixture is poured in mould, mould is put into heating 2h in 100 DEG C of baking oven, raises for case temperature to 120 DEG C of recurring 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 there-necked flask, be warming up to 80 DEG C of reaction 5h, after having reacted, be cooled to room temperature, product is transferred to burning In cup, add normal hexane cleaning, stir 5min with Glass rod, so that solid product is completely dispersed, sucking filtration, repeats aforesaid operations three Secondary it is ensured that in product unreacted hexamethylene diisocyanate clean up.By the 30 DEG C of vacuum of solid product after cleaning It is dried to constant weight.Stand-by with DMSO dissolving (every 100mL DMSO dissolves 20g HDI-BDO-HDI chain extender) after drying；

(2) a certain amount of 100ml PEG-600 is added in vacuum response bottle, vaccum dewatering 2h, eliminating water under the conditions of 90 DEG C After be cooled to room temperature, then add 1mol L- lactide and 1.1mol caprolactone in vacuum response bottle, add octoate catalyst Stannous (catalyst quality accounts for the 0.5% of reaction raw materials gross mass), will be airtight for vacuum response bottle after evacuation, 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 dewatering, After stirring, the dropwise DMSO solution of Deca HDI-BDO-HDI chain extender.After being added dropwise to complete, react 5h at 80 DEG C.Reacted Cheng Zhong, reactant viscosity can increase, and can suitably add some solvent dioxane.By the solution that completes of reaction be poured slowly into from Settle in sub- water, sucking filtration, products therefrom is dried in vacuum drying oven 48h, as polylactic acid-polyurethane copolymer；

A3：Polylactic acid-the polyurethane copolymer (piperazinedione acid percent grafting is 2%) of grafting piperazinedione acid

(2) a certain amount of 100ml PEG-600 is added in vacuum response bottle, vaccum dewatering 2h, eliminating water under the conditions of 90 DEG C After be cooled to room temperature, then add 1mol L- lactide and 1.1mol caprolactone in vacuum response bottle, add octoate catalyst Stannous (catalyst quality accounts for the 0.5% of reaction raw materials gross mass), will be airtight for vacuum response bottle after evacuation, 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 dewatering, After stirring, the dropwise DMSO solution of Deca HDI-BDO-HDI chain extender.After being added dropwise to complete, react 5h at 80 DEG C.Reacted Cheng Zhong, reactant viscosity can increase, and can suitably add some solvent dioxane.By the solution that completes of reaction be poured slowly into from Settle in sub- water, sucking filtration, products therefrom is dried in vacuum drying oven 48h, as polylactic acid-polyurethane copolymer；

(4) polymer in step (3) is warming up to 120 DEG C, solid is in molten condition vacuumizing and defoaming, will mix immediately all Even mixture is poured in mould, mould is put into heating 2h in 100 DEG C of baking oven, raises for case temperature to 120 DEG C of recurring 2h, the demoulding, that is, obtain spherical rubber container.

A4：The compositionss that the polylactic acid-polyurethane copolymer of grafting piperazinedione acid is obtained with the blending of tetrafluoroethene granule (tetrafluoroethene granule pore size is 2 μm, and number-average molecular weight is 10000, and piperazinedione acid percent grafting is 2%)

(4) add piperazinedione acid polydactyl acid-polyurethane copolymer in there-necked flask, be warming up to 120 DEG C, solid In molten condition, add 2g polytetrafluoroethylgranule granule, stir 0.5h, solid is in molten condition vacuumizing and defoaming, will mix immediately Uniform mixture is poured in mould, mould is put into heating 2h in 100 DEG C of baking oven, raises ripe again to 120 DEG C for case temperature Change 2h, the demoulding, that is, obtain spherical rubber container.

A5：The group that the polylactic acid-polyurethane copolymer of grafting piperazinedione acid is obtained with the blending of varicosity tetrafluoroethene granule Compound (varicosity tetrafluoroethene granule pore size is 0.2 μm, and number-average molecular weight is 10000, and piperazinedione acid percent grafting is 2%)

(4) add piperazinedione acid polydactyl acid-polyurethane copolymer in there-necked flask, be warming up to 120 DEG C, solid In molten condition, add 2g expanded polytetrafluoroethylsealing granule, stir 0.5h, solid is in molten condition vacuumizing and defoaming, immediately will The mixture of mix homogeneously is poured in mould, mould is put into heating 2h in 100 DEG C of baking oven, raises for case temperature to 120 DEG C Recurring 2h, the demoulding, that is, obtain spherical rubber container.

A6：Polylactic acid-the polyurethane copolymer of grafting piperazinedione acid mixes, with silica dioxide granule, the compositionss (two obtaining Silicon oxide pore size 10nm；Piperazinedione acid percent grafting is 2%)

Preparation method is as follows：

(1) silica dioxide granule:Transition metal salt ZnCl by 0.3g₂Being added to 100mL substance withdrawl syndrome is In the dilute hydrochloric acid solution of 2mol/L, slaine is made to be dissolved completely in aqueous solution in 35 DEG C of steady temperatures with magnetic agitation, so 2.5g nonionic surfactant ether oxygen class surfactant P123 is added backward in above-mentioned system.In 35 DEG C of constant temperature, magnetic force stirs Mix 3 hours, afterwards to Deca 5.6mL tetraethyl orthosilicate (TEOS) in above-mentioned system, continue stirring 6 hours afterwards, under room temperature Standing 24 hours, pours out supernatant, remaining white depositions is transferred in crucible.Last calcining 3 hours under the conditions of 550 DEG C (batch-type furnace is per minute to heat up 5 DEG C).

(2) 1 mole of 1,4- butanediol (BDO) and 4 moles of hexamethylene diisocyanates (HDI) are added to 500ml tri- In mouth flask, it is warming up to 80 DEG C of reaction 5h, after having reacted, is cooled to room temperature, product is transferred in beaker, add just own Alkane cleans, and stirs 5min with Glass rod, so that solid product is completely dispersed, sucking filtration, repeats aforesaid operations three times it is ensured that in product Unreacted hexamethylene diisocyanate cleans up, and 30 DEG C of solid product after cleaning is dried under vacuum to constant weight, does Stand-by with DMSO dissolving (every 100mL DMSO dissolves 20g HDI-BDO-HDI chain extender) after dry；

(3) a certain amount of 100ml PEG-600 is added in vacuum response bottle, vaccum dewatering 2h, eliminating water under the conditions of 90 DEG C After be cooled to room temperature, then add 1mol L- lactide and 1.1mol caprolactone in vacuum response bottle, add octoate catalyst Stannous (catalyst quality accounts for the 0.5% of reaction raw materials gross mass), will be airtight for vacuum response bottle after evacuation, 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 dewatering, After stirring, the dropwise DMSO solution of Deca HDI-BDO-HDI chain extender.After being added dropwise to complete, react 5h at 80 DEG C.Reacted Cheng Zhong, reactant viscosity can increase, and can suitably add some solvent dioxane.By the solution that completes of reaction be poured slowly into from Settle in sub- water, sucking filtration, products therefrom is dried in vacuum drying oven 48h, as polylactic acid-polyurethane copolymer；

(4) polylactic acid-polyurethane copolymer is immersed the hydrogenperoxide steam generator of 2V 2vt% acetum and 2V 5wt% In, it is slowly added to be dissolved in piperazinedione acid (0.5g) solution of 5ml methanol, after reaction completely, use 10wt%NaOH aqueous solution Adjust pH be in neutrality after filter, soaking to trapped substance, washing, sucking filtration, products therefrom is dried 48h in vacuum drying oven, It is piperazinedione acid polydactyl acid-polyurethane copolymer；

(5) add piperazinedione acid polydactyl acid-polyurethane copolymer by weight in there-necked flask, be warming up to 120 DEG C, solid is in molten condition, adds 2g silica dioxide granule, is stirred for 1h, and solid is in molten condition vacuumizing and defoaming, stands Will pour in mould the mixture of mix homogeneously, mould is put into heating 2h in 100 DEG C of baking oven, raise for case temperature extremely 120 DEG C of recurring 2h, the demoulding, that is, obtain spherical rubber container.A7：Polylactic acid-the polyurethane copolymer of grafting piperazinedione acid Mix compositionss (the mesoporous silica particles pore size 1.5nm obtaining with mesoporous silica particles；Piperazinedione acid grafting Rate is 2%)

(3) polylactic acid-polyurethane copolymer is immersed the hydrogenperoxide steam generator of 2V 2vt% acetum and 2V 5wt% In, it is slowly added to be dissolved in piperazinedione acid (0.5g) solution of 5ml methanol, after reaction completely, use 10wt%NaOH aqueous solution Adjust pH be in neutrality after filter, soaking to trapped substance, washing, sucking filtration, products therefrom is dried 48h in vacuum drying oven, It is piperazinedione acid polydactyl acid-polyurethane copolymer；(4) add the modified poly- breast of piperazinedione acid in there-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, immediately the mixture of mix homogeneously is poured in mould, mould is put in 100 DEG C of baking oven Heating 2h, raises for case temperature to 120 DEG C of recurring 2h, the demoulding, that is, obtains spherical rubber container.

A8：Polylactic acid-the polyurethane copolymer of grafting piperazinedione acid and polytetrafluoroethylgranule granule, silica dioxide granule mix (tetrafluoroethene granule pore size is 2 μm to the compositionss obtaining, and number-average molecular weight is 10000, and silicon dioxide aperture size is 10nm, piperazinedione acid percent grafting is 2%)

(4) add piperazinedione acid polydactyl acid-polyurethane copolymer in there-necked flask, be warming up to 120 DEG C, solid In molten condition, add 1g polytetrafluoroethylgranule granule, stir 0.5h, add 1g silica dioxide granule, be stirred for 1h, solid is in molten Melt state vacuumizing and defoaming, pour the mixture of mix homogeneously in mould into immediately, mould is put into heating in 100 DEG C of baking oven 2h, raises for case temperature to 120 DEG C of recurring 2h, the demoulding, that is, obtains spherical rubber container.

Silica dioxide granule preparation method is with A6 step (1).

A9：Polylactic acid-polyurethane copolymer expanded PTFE the granule of grafting piperazinedione acid, silica dioxide granule (varicosity tetrafluoroethene granule pore size is 0.2 μm to the mixed compositionss obtaining, and number-average molecular weight is 10000, silicon dioxide aperture Size is 10nm, and piperazinedione acid percent grafting is 2%)

(4) add piperazinedione acid polydactyl acid-polyurethane copolymer in there-necked flask, be warming up to 120 DEG C, solid In molten condition, add 1g expanded polytetrafluoroethylsealing granule, stir 0.5h, add 1g silica dioxide granule, be stirred for 1h, solid In molten condition vacuumizing and defoaming, immediately the mixture of mix homogeneously is poured in mould, mould is put in 100 DEG C of baking oven Heating 2h, raises for case temperature to 120 DEG C of recurring 2h, the demoulding, that is, obtains spherical rubber container.

Silica dioxide granule preparation method is with A6 step (1).

A10：Polylactic acid-the polyurethane copolymer of grafting piperazinedione acid and expanded PTFE granule, micropore dioxy Silicon carbide particle mixes the compositionss obtaining, and (varicosity tetrafluoroethene granule pore size is 0.2 μm, and number-average molecular weight is 10000, micropore Silicon dioxide aperture size is 1.5nm, and piperazinedione acid percent grafting is 2%)

(2) 100ml PEG-600 is added in vacuum response bottle, vaccum dewatering 2h under the conditions of 90 DEG C, lowers the temperature after eliminating water To room temperature, then add 1mol L- lactide and 1.1mol caprolactone in vacuum response bottle, add octoate catalyst stannous (catalyst quality accounts for the 0.5% of reaction raw materials gross mass), will be airtight for vacuum response bottle after evacuation, 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 dewatering, stirring After uniformly, the dropwise DMSO solution of Deca HDI-BDO-HDI chain extender.After being added dropwise to complete, react 5h at 80 DEG C.Course of reaction In, reactant viscosity can increase, and can suitably add some solvent dioxane.The solution that reaction is completed is poured slowly into deionization Settle in water, sucking filtration, products therefrom is dried in vacuum drying oven 48h, as polylactic acid-polyurethane copolymer；

A11：Polylactic acid-polyurethane copolymer and expanded PTFE granule, mesoporous silica particles mix and obtain (varicosity tetrafluoroethene granule pore size is 0.2 μm to compositionss, and number-average molecular weight is 10000, mesoporous silica pore size For 1.5nm)

(3) add polylactic acid-polyurethane copolymer in there-necked flask, be warming up to 120 DEG C, solid is in molten condition, plus Enter 1g expanded polytetrafluoroethylsealing granule, stir 0.5h, add 1g mesoporous silica particles, be stirred for 1h, solid is in molten State vacuumizing and defoaming, pours the mixture of mix homogeneously in mould into immediately, mould is put into heating 2h in 100 DEG C of baking oven, Raise for case temperature to 120 DEG C of recurring 2h, the demoulding, that is, obtain spherical rubber container.

A12：Polylactic acid-the polyurethane copolymer of grafting piperazinedione acid and expanded PTFE granule, micropore dioxy Silicon carbide particle mixes the compositionss obtaining, and (varicosity tetrafluoroethene granule pore size is 0.2 μm, and number-average molecular weight is 10000, micropore Silicon dioxide aperture size is 1nm, and piperazinedione acid percent grafting is 3%)

(3) polylactic acid-polyurethane copolymer is immersed the hydrogenperoxide steam generator of 2V 2vt% acetum and 2V 5wt% In, it is slowly added to be dissolved in piperazinedione acid (0.8g) solution of 5ml methanol, after reaction completely, use 10wt%NaOH aqueous solution Adjust pH be in neutrality after filter, soaking to trapped substance, washing, sucking filtration, products therefrom is dried 48h in vacuum drying oven, It is piperazinedione acid polydactyl acid-polyurethane copolymer；

A13：Polylactic acid

Preparation method is as follows：(1) 100ml PEG-600 is added in vacuum response bottle, vaccum dewatering under the conditions of 90 DEG C 2h, is cooled to room temperature after eliminating water, then adds 1mol L- lactide and 1.1mol caprolactone in vacuum response bottle, adds and urges Agent stannous octoate (catalyst quality accounts for the 0.5% of reaction raw materials gross mass), will be airtight for vacuum response bottle after evacuation, Under the conditions of 140 DEG C, reaction 24h prepares prepolymer.

(2) add polylactic acid prepolymer in there-necked flask, be warming up to 120 DEG C, solid is in molten condition, solid is in melting State vacuumizing and defoaming, pours the mixture of mix homogeneously in mould into immediately, mould is put into heating in 100 DEG C of baking oven 2h, raises for case temperature to 120 DEG C of recurring 2h, the demoulding, that is, obtains spherical rubber container.

A14:Polylactic acid and expanded PTFE granule, mesoporous silica particles mix the compositionss (varicosity four obtaining Fluorothene granule pore size is 0.2 μm, and number-average molecular weight is 10000, and mesoporous silica pore size is 1nm)

(2) add polylactic acid performed polymer in there-necked flask, be warming up to 120 DEG C, solid is in molten condition, add 1g expanded Polytetrafluoroethylgranule granule, stirs 0.5h, adds 1g mesoporous silica particles, is stirred for 1h, and solid is in molten condition evacuation Deaeration, pours the mixture of mix homogeneously in mould into immediately, mould is put into heating 2h in 100 DEG C of baking oven, raises and supply case Temperature to 120 DEG C of recurring 2h, the demoulding, that is, obtains spherical rubber container.

B1:Band

C1:Band stopple

In embodiment, when carrying out packing Flos Rosae Rugosae, in modified polyurethane composition, store water.

Embodiment 1

Combined by A3, B1, C1, obtain combination container, pack Flos Rosae Rugosae.

Embodiment 2

Combined by A4, B1, C1, obtain combination container, pack Flos Rosae Rugosae.

Embodiment 3

Combined by A5, B1, C1, obtain combination container, pack Flos Rosae Rugosae.

Embodiment 4

Combined by A6, B1, C1, obtain combination container, pack Flos Rosae Rugosae.

Embodiment 5

Combined by A7, B1, C1, obtain combination container, pack Flos Rosae Rugosae.

Embodiment 6

Combined by A8, B1, C1, obtain combination container, pack Flos Rosae Rugosae.

Embodiment 7

Combined by A9, B1, C1, obtain combination container, pack Flos Rosae Rugosae.

Embodiment 8

Combined by A10, B1, C1, obtain combination container, pack Flos Rosae Rugosae.

Embodiment 9

Combined by A11, B1, C1, obtain combination container, pack Flos Rosae Rugosae.

Embodiment 10

Combined by A12, B1, C1, obtain combination container, pack Flos Rosae Rugosae.

Comparative example 1

Combined by A1, B1, C1, obtain combination container, pack Flos Rosae Rugosae.

Comparative example 2

Combined by A2, B1, C1, obtain combination container, pack Flos Rosae Rugosae.

Comparative example 3

Combined by A13, B1, C1, obtain combination container, pack Flos Rosae Rugosae.

Comparative example 4

Combined by A14, B1, C1, obtain combination container, pack Flos Rosae Rugosae.

Comparative example 5

Combined by B1, C1, pack Flos Rosae Rugosae.

Flos Rosae Rugosae to above-described embodiment 1～10 and comparative example 1～5 packaging and modified polyurethane composition A enter to advance Row test, method of testing is as follows：

1st, fresh keeping time：, at 18 degree about, air humidity 90%, with the combination container bag of above-described embodiment preparation for room temperature Dress, observes the life-span of Flos Rosae Rugosae；

2nd, bacteriostasis rate：Dipping culture rule is that sample is immersed in bacteria suspension, after culture a period of time, by flat The method that plate counts carries out count plate, and then calculates antibiotic rate, the antibiotic rate=(bacterium number-antimicrobial sample on blank sample On bacterium number) bacterium number × 100% on/blank sample；

3rd, degrade：The A sample (1.0cm × 1.0cm, about 0.25g) of multiple embodiment preparations of precise is thrown respectively The Borax buffering entered equipped with 50mL normal saline solution, the acetic acid of 50mL pH=4, sodium acetate buffer and pH=9.18 is molten 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.

Table 1 the performance test results

In sum it is known that, modified polyurethane composition and spherical polyurethane, spherical poly- breast in the flower arrangement device of the present invention Acid, be not grafted piperazinedione acid, blending polytetrafluoroethylgranule granule and silica dioxide granule contrasted, the flower arrangement device of the present invention In flower packaging, fresh-keeping, transport, there is very big advantage in terms of environmental protection.

Above-mentioned example is merely illustrative, for explaining some features of the feature of the present invention.Appended claim It is intended to the scope as wide as possible requiring to be contemplated that, and embodiments as presented herein is only according to all possible embodiment The embodiment of the selection of combination explanation.Therefore, the purpose of applicant is appended claim not by the explanation present invention The example of feature selectional restriction, and the progress in science and technology will be formed due to language performance inaccurate reason and not The possible equivalent being presently considered or son are replaced, and these changes also should be interpreted by appended in the conceived case Claim covers.

Claims

1. a kind of flower arrangement device is it is characterised in that it is by carrying the spherical rubber container of cervical region, band stopple and band to form, described band Stopple fills in band cervical region spherical rubber container neck interior, and is enclosed within solid outside band cervical region spherical rubber container cervical region by band Fixed, described band stopple top is flushed with band cervical region spherical rubber container cervical region top.

2. flower arrangement device described in claim 1 is it is characterised in that the spherical rubber container material of described band cervical region is modified polyurethane Compositionss, band material is rubber, and band stopple material is EVA foam or high-elastic PE, and wherein, modified polyurethane composition at least wraps Containing polylactic acid, polyurethane, piperazinedione acid and expanded PTFE.

3. flower arrangement device described in claim 2 is it is characterised in that described modified polyurethane composition also comprises nanoporous silica Silicon.

4. flower arrangement device described in claim 3 is it is characterised in that described modified polyurethane composition is common by polylactic acid-polyurethane Grafting piperazinedione acid on polymers, is then obtained with expanded PTFE, mesoporous silica blending.

5. described in claim 4 flower arrangement device it is characterised in that on described polylactic acid-polyurethane copolymer piperazinedione acid Percent grafting is 1～3%.

6. described in claim 4 flower arrangement device it is characterised in that on described polylactic acid-polyurethane copolymer piperazinedione acid Percent grafting is 1～2%.

7. flower arrangement device described in claim 1 is it is characterised in that the described top bore with the spherical rubber container of cervical region is 1.5 ～3cm, top is 2～3cm with the distance of spherical upper end.

8. flower arrangement device described in claim 1 is it is characterised in that the width of described band is 2～3cm.

9. it is characterised in that described a diameter of 5～8cm with stopple, thickness is 1～2cm to flower arrangement device described in claim 1, Aperture 0.05～0.08cm.

10. described in claim 1～9 flower arrangement device it is characterised in that described flower arrangement device be applied to flowers packaging, fresh-keeping, Storage and transport.