CN106398183A

CN106398183A - Preparation method of ikebana device

Info

Publication number: CN106398183A
Application number: CN201610791885.0A
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: CN106398183B

Abstract

The invention provides a preparation method of an ikebana device. The preparation method comprises the following steps: (1) inserting a porous plug with flowers into the neck portion of a neck containing spherical rubber container filled with water; and (2) fixing the contact surface between the porous plug and the neck containing spherical rubber container by a binding belt; wherein the neck containing spherical rubber container is made of a polyurethane composition, which at least comprises polylactic acid, polyurethane, piperazine dione acid, expanded polytetrafluoroethylene, and microporous silica; the binding belt is made of rubber; and the porous plug is made of EVA foam or high elasticity PE. The provided ikebana device has great advantages in flower package, flower fresh-keeping, flower transportation, and environment protection.

Description

A kind of preparation method of flower arrangement device

Technical field

A kind of the invention belongs to preparation method of flower arrangement device, more particularly it relates to flower arrangement device composition material Preparation method.

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 provide a kind of preparation method of flower arrangement device, this flower arrangement device is packed, protected in flower Fresh, transport, environmental protection aspect there is very big advantage.

Content of the invention

In order to solve the above problems, the present invention provides a kind of preparation method of flower arrangement device, comprises the steps：

(1) put into, by be inserted with flowers, the neck location with the spherical rubber container of cervical region being marked with water with stopple；

(2) band fixing band stopple and band cervical region spherical rubber container neck contacts face are used；

Wherein, described band cervical region spherical rubber container material is modified polyurethane composition, and it includes at least polylactic acid, gathers Urethane, piperazinedione acid, expanded PTFE and mesoporous silica；Band material is rubber；Band stopple material steeps for EVA Cotton or high-elastic PE.

In one embodiment, described band cervical region spherical rubber container material is modified polyurethane composition, its preparation Method comprises the steps：

(1) pre-polymerization：Add diisocyanate and dihydroxylic alcohols by weight in reaction bulb, be warming up to 80～100 DEG C of reactions 3 ～8h, is cooled to room temperature, filters, 30～40 DEG C of dryings, obtains polyurethane prepolymer；

(2) copolymerization：Add by weight in lactide, caprolactone and catalyst vacuum response bottle, under vacuum condition, 130 ～150 DEG C of reaction 20～30h prepare polylactic acid prepolymer, are cooled to 80 DEG C, add polyurethane in PEG-600 and step (1) pre- Polymers, 80 DEG C of reaction 3～6h, add deionized water to be settled, filter, be dried, obtain polylactic acid-polyurethane copolymer；

(3) modified：Solid in step (2) hydrogenperoxide steam generator of 2vt% acetum and 5wt% is dissolved, presses Weight portion add piperazinedione acid solution, react 3～8h, with 10wt%NaOH aqueous solution adjust pH be in neutrality after filter, be dried；

(4) it is blended：Under the conditions of in step (3), solid is warming up to 110～140 DEG C, solid sequentially adds after being completely dissolved Expanded polytetrafluoroethylsealing granule and mesoporous silica particles, after stirring, solid is in molten condition vacuumizing and defoaming, immediately The mixture of mix homogeneously is poured in mould, mould is put into heating 2h in 100 DEG C of baking oven, raise for case temperature to 120 DEG C recurring 2h, the demoulding, that is, obtain spherical rubber container.

In one embodiment, the preparation method of described modified polyurethane composition, calculates by weight, at least includes 60～75 weight portion diisocyanate；5～12 weight portion dihydroxylic alcohols；10～20 weight portion lactides；Oneself is interior for 10～20 weight portions Ester；0.05～0.5 weight portion expanded PTFE；0.05～0.5 weight portion mesoporous silica.

In one embodiment, described diisocyanate is at least hexamethylene diisocyanate, 4,4- diphenylmethyl Alkane diisocyanate, Toluene-2,4-diisocyanate, 4- diisocyanate, 1,5- naphthalene diisocyanate, PPDI, isophorone two are different One or more of cyanate.

In one embodiment, described dihydroxylic alcohols are at least BDO, diethylene glycol, Polyethylene Glycol, polyester two One or more in first alcohol, polyether Glycols.

In one embodiment, described be modified as on polylactic acid-polyurethane copolymer grafting piperazinedione acid, it connects Branch rate is 1～3%.

In one embodiment, described expanded polytetrafluoroethylsealing and the mass ratio of mesoporous silica are (0.5～2)： 1.

In one embodiment, the number-average molecular weight of described expanded polytetrafluoroethylsealing is 5000～30000.

In one embodiment, the pore size of described expanded polytetrafluoroethylsealing is 0.1～1.5 μm.

In one embodiment, the pore size of described mesoporous silica is 1nm～2nm.

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.

The present invention provides a kind of preparation method of flower arrangement device, comprises the steps：

In one embodiment, described diisocyanate is at least hexamethylene diisocyanate, 4,4- diphenylmethyl Alkane diisocyanate, Toluene-2,4-diisocyanate, 4- diisocyanate, 1,5- naphthalene diisocyanate, PPDI, isophorone two are different One or more of cyanate；Preferably, described diisocyanate is at least hexamethylene diisocyanate, 4,4- diphenyl Methane diisocyanate, Toluene-2,4-diisocyanate, one of 4- diisocyanate, PPDI, isophorone diisocyanate Or it is multiple；Preferably, described diisocyanate is at least hexamethylene diisocyanate, 4,4- diphenylmethane diisocyanate One or more of ester, PPDI, isophorone diisocyanate.

In one embodiment, described dihydroxylic alcohols are at least BDO, diethylene glycol, Polyethylene Glycol, polyester two One or more in first alcohol, polyether Glycols；Preferably, described dihydroxylic alcohols are at least BDO, diethylene glycol, poly- second two One or more in alcohol；Preferably, described dihydroxylic alcohols are at least BDO, one or more in diethylene glycol.

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

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, and hard section is then by aliphatic (such as Isophorone diisocyanate) or alicyclic diisocyanate and small molecule glycol composition, thus obtain degradable, avirulence Polyurethane.Ester due to this kind of polyurethane soft section is typically synthesized with small-molecule substance, and susceptible to hydrolysis, after hydrolysis Small molecule can also be become.

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.

In one embodiment, described expanded polytetrafluoroethylsealing and the mass ratio of mesoporous silica are (0.5～2)： 1；Preferably, described expanded polytetrafluoroethylsealing and the mass ratio of mesoporous silica are (0.5～1.5)：1.

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

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.

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 hc 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.

In one embodiment, the pore size of described mesoporous silica is 1nm～2nm.

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 1.3-2nm；

(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_2-8-2Surfactant molecule structure formula

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 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 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：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%)

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, magnetic force stirs in 35 DEG C of constant temperature in above-mentioned system 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, finally calcines 3 hours under the conditions of 550 DEG C (batch-type furnace is per minute to heat up 5 DEG C)；

(2) 9 weight portions 1,4- butanediol (BDO) are added to 68 weight portion hexamethylene diisocyanates (HDI) In 250ml there-necked 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 normal hexane cleaning, stir 5min with Glass rod, so that solid product is completely dispersed, sucking filtration, repeats aforesaid operations three times, really Protect unreacted hexamethylene diisocyanate in product to clean up, 30 DEG C of solid product after cleaning is dried under vacuum to Constant weight, stand-by with DMSO dissolving (every 100mL DMSO dissolves 20g HDI-BDO-HDI chain extender) after being dried；

(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 15 weight portion L- lactides and 13 parts by weight of caprolactone in vacuum response bottle, add catalysis 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, 140 Under the conditions of DEG C, reaction 24h prepares prepolymer, and after the completion of reaction, prepolymer is cooled to 80 DEG C, after adding 60ml vaccum dewatering PEG-600, after stirring, the dropwise DMSO solution of Deca HDI-BDO-HDI chain extender, after being added dropwise to complete, reacts at 80 DEG C 5h, in course of reaction, reactant viscosity can increase, and can suitably add some solvent dioxane, and the solution that reaction is completed delays Slowly pour sedimentation, sucking filtration in deionized water into, products therefrom is dried in vacuum drying oven 48h, as polylactic acid-polyurethane is common Polymers；

(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 (0.05 weight portion) solution of 5ml methanol, after reaction completely, use 10wt%NaOH It is in filter after neutrality that aqueous solution adjusts pH, washing soaking to trapped substance, sucking filtration, and products therefrom is dry in vacuum drying oven Dry 48h, as piperazinedione acid polydactyl acid-polyurethane copolymer；

(5) add piperazinedione acid polydactyl acid-polyurethane copolymer in there-necked flask, be warming up to 120 DEG C, solid In molten condition, add 0.1 weight portion polytetrafluoroethylgranule granule, stir 0.5h, add 0.1 parts by weight of silica granule, then Stirring 1h, solid is in molten condition vacuumizing and defoaming, pours the mixture of mix homogeneously in mould into immediately, mould is put into Heat 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.

A2：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%)

Preparation method is as follows：(1) by 9 weight portions 1,4- butanediol (BDO) and 68 weight portion hexamethylene diisocyanates (HDI) it is added in 250ml there-necked flask, be warming up to 80 DEG C of reaction 5h, after having reacted, be cooled to room temperature, product is turned Move on in beaker, add normal hexane cleaning, stir 5min with Glass rod, so that solid product is completely dispersed, sucking filtration, repeats above-mentioned Operate three times it is ensured that unreacted hexamethylene diisocyanate cleans up in product, by the solid product 30 after cleaning DEG C it is dried under vacuum to constant weight, stand-by with DMSO dissolving (every 100mL DMSO dissolves 20g HDI-BDO-HDI chain extender) after being dried；

(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 15 weight portion L- lactides and 13 parts by weight of caprolactone in vacuum response bottle, add catalysis 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, 140 Under the conditions of DEG C, reaction 24h prepares prepolymer, and after the completion of reaction, prepolymer is cooled to 80 DEG C, after adding 60ml vaccum dewatering PEG-600, after stirring, the dropwise DMSO solution of Deca HDI-BDO-HDI chain extender, after being added dropwise to complete, reacts at 80 DEG C 5h, in course of reaction, reactant viscosity can increase, and can suitably add some solvent dioxane.The solution that reaction is completed delays Slowly pour sedimentation, sucking filtration in deionized water into, products therefrom is dried in vacuum drying oven 48h, as polylactic acid-polyurethane is common Polymers；

(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 (0.05 weight portion) solution of 5ml methanol, after reaction completely, use 10wt%NaOH It is in filter after neutrality that aqueous solution adjusts pH, washing soaking to trapped substance, sucking filtration, and products therefrom is dry in vacuum drying oven Dry 48h, as 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 0.1 weight portion expanded polytetrafluoroethylsealing granule, stir 0.5h, add 0.1 parts by weight of silica Grain, is stirred for 1h, and solid is in molten condition vacuumizing and defoaming, pours the mixture of mix homogeneously in mould into immediately, by mould 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.

Silica dioxide granule preparation method is with A1 step (1).

A3：Polylactic acid-the polyurethane copolymer of grafting piperazinedione acid and expanded PTFE granule, nanoporous silica Silicon grain mixes the compositionss obtaining, and (varicosity tetrafluoroethene granule pore size is 0.2 μm, and number-average molecular weight is 10000, micropore two Silicon oxide pore size is 1nm, and piperazinedione acid percent grafting is 2%)

Preparation method is as follows：(1) by 9 weight portions 1,4- butanediol (BDO) and 68 weight portion hexamethylene diisocyanates (HDI) it is added in 250ml there-necked flask, be warming up to 80 DEG C of reaction 5h, after having reacted, be cooled to room temperature, product is turned Move on in beaker, add normal hexane cleaning, stir 5min with Glass rod, so that solid product is completely dispersed, sucking filtration, repeats above-mentioned Operate three times it is ensured that unreacted hexamethylene diisocyanate cleans up in product.By the solid product 30 after cleaning DEG C it is dried under vacuum to constant weight, stand-by with DMSO dissolving (every 100mL DMSO dissolves 20g HDI-BDO-HDI chain extender) after being dried；

(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 15 weight portion L- lactides and 13 parts by weight of 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, is cooled to 80 DEG C under vacuum, after adding 60ml vaccum dewatering PEG-600, after stirring, the dropwise DMSO solution of Deca HDI-BDO-HDI chain extender, after being added dropwise to complete, reacts at 80 DEG C 5h, in course of reaction, reactant viscosity can increase, and can suitably add some solvent dioxane, and the solution that reaction is completed delays Slowly pour sedimentation, sucking filtration in deionized water into, products therefrom is dried in vacuum drying oven 48h, as polylactic acid-polyurethane is common Polymers；

(4) add piperazinedione acid polydactyl acid-polyurethane copolymer in there-necked flask, be warming up to 120 DEG C, solid In molten condition, add 0.1 weight portion expanded polytetrafluoroethylsealing granule, stir 0.5h, add 0.1 weight portion mesoporous silica Granule, is stirred for 1h, and solid is in molten condition vacuumizing and defoaming, pours the mixture of mix homogeneously in mould into immediately, by mould Have in the baking oven put into 100 DEG C and heat 2h, raise for case temperature to 120 DEG C of recurring 2h, the demoulding, that is, obtain spherical rubber and hold Device.

A4：Polylactic acid-the polyurethane copolymer of grafting piperazinedione acid and expanded PTFE granule, nanoporous silica Silicon grain mixes the compositionss obtaining, and (varicosity tetrafluoroethene granule pore size is 0.2 μm, and number-average molecular weight is 5000, micropore two Silicon oxide pore size is 1nm, and piperazinedione acid percent grafting is 1%)

(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 15 weight portion L- lactides and 13 parts by weight of caprolactone in vacuum response bottle, add catalysis 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, 140 Under the conditions of DEG C, reaction 24h prepares prepolymer, and after the completion of reaction, prepolymer is cooled to 80 DEG C, after adding 60ml vaccum dewatering PEG-600, after stirring, the dropwise DMSO solution of Deca HDI-BDO-HDI chain extender, after being added dropwise to complete, reacts at 80 DEG C 5h, in course of reaction, reactant viscosity can increase, and can suitably add some solvent dioxane, and the solution that reaction is completed delays Slowly pour sedimentation, sucking filtration in deionized water into, products therefrom is dried in vacuum drying oven 48h, as polylactic acid-polyurethane is common Polymers；

A5：Polylactic acid-the polyurethane copolymer of grafting piperazinedione acid and expanded PTFE granule, nanoporous silica Silicon grain mixes the compositionss obtaining, and (varicosity tetrafluoroethene granule pore size is 0.2 μm, and number-average molecular weight is 10000, micropore two Silicon oxide pore 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 (0.1 weight portion) solution of 5ml methanol, after reaction completely, use 10wt%NaOH water Solution adjust pH be in neutrality after filter, soaking to trapped substance, washing, sucking filtration, by products therefrom in vacuum drying oven be dried 48h, as piperazinedione acid polydactyl acid-polyurethane copolymer；

A6：Polylactic acid-the polyurethane copolymer of grafting piperazinedione acid and expanded PTFE granule, nanoporous silica Silicon grain mixes the compositionss obtaining, and (varicosity tetrafluoroethene granule pore size is 0.2 μm, and number-average molecular weight is 10000, micropore two Silicon oxide pore size is 1nm, and piperazinedione acid percent grafting is 2%)

Preparation method is as follows：(1) by 5 weight portions 1,4- butanediol (BDO) and 60 weight portion hexamethylene diisocyanates (HDI) it is added in 250ml there-necked flask, be warming up to 80 DEG C of reaction 5h, after having reacted, be cooled to room temperature, product is turned Move on in beaker, add normal hexane cleaning, stir 5min with Glass rod, so that solid product is completely dispersed, sucking filtration, repeats above-mentioned Operate three times it is ensured that unreacted hexamethylene diisocyanate cleans up in product, by the solid product 30 after cleaning DEG C it is dried under vacuum to constant weight, stand-by with DMSO dissolving (every 100mL DMSO dissolves 20g HDI-BDO-HDI chain extender) after being dried；

(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 10 weight portion L- lactides and 10 parts by weight of 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, is cooled to 80 DEG C under vacuum, adds the PEG-600 after 60ml vaccum dewatering, and stirring is all After even, the dropwise DMSO solution of Deca HDI-BDO-HDI chain extender, after being added dropwise to complete, react 5h at 80 DEG C, in course of reaction, Reactant viscosity can increase, and can suitably add some solvent dioxane, and the solution that reaction is completed is poured slowly into deionized water Middle sedimentation, sucking filtration, products therefrom is dried in vacuum drying oven 48h, as polylactic acid-polyurethane copolymer；

A7：Polylactic acid-the polyurethane copolymer of grafting piperazinedione acid and expanded PTFE granule, nanoporous silica Silicon grain mixes the compositionss obtaining, and (varicosity tetrafluoroethene granule pore size is 0.2 μm, and number-average molecular weight is 10000, micropore two Silicon oxide pore size is 1nm, and piperazinedione acid percent grafting is 2%)

Preparation method is as follows：(1) by 15 weight portions 1,4- butanediol (BDO) and 75 weight portion hexamethylene diisocyanates (HDI) it is added in 250ml there-necked flask, be warming up to 80 DEG C of reaction 5h, after having reacted, be cooled to room temperature, product is turned Move on in beaker, add normal hexane cleaning, stir 5min with Glass rod, so that solid product is completely dispersed, sucking filtration, repeats above-mentioned Operate three times it is ensured that unreacted hexamethylene diisocyanate cleans up in product, by the solid product 30 after cleaning DEG C it is dried under vacuum to constant weight, stand-by with DMSO dissolving (every 100mL DMSO dissolves 20g HDI-BDO-HDI chain extender) after being dried；

(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 20 weight portion L- lactides and 20 parts by weight of 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 reaction terminates, is cooled to 80 DEG C under vacuum, after adding 60ml vaccum dewatering PEG-600, after stirring, the dropwise DMSO solution of Deca HDI-BDO-HDI chain extender, after being added dropwise to complete, reacts at 80 DEG C 5h, in course of reaction, reactant viscosity can increase, and can suitably add some solvent dioxane, and the solution that reaction is completed delays Slowly pour sedimentation, sucking filtration in deionized water into, products therefrom is dried in vacuum drying oven 48h, as polylactic acid-polyurethane is common Polymers；

A8：Polylactic acid-the polyurethane copolymer of grafting piperazinedione acid and expanded PTFE granule, nanoporous silica Silicon grain mixes the compositionss obtaining, and (varicosity tetrafluoroethene granule pore size is 0.2 μm, and number-average molecular weight is 10000, micropore two Silicon oxide pore size is 1nm, and piperazinedione acid percent grafting is 2%)

Preparation method is as follows：(1) by 9 weight portion diethylene glycols (BDO) and 68 weight portion hexamethylene diisocyanates (HDI) it is added in 250ml there-necked flask, be warming up to 80 DEG C of reaction 5h, after having reacted, be cooled to room temperature, product is turned Move on in beaker, add normal hexane cleaning, stir 5min with Glass rod, so that solid product is completely dispersed, sucking filtration, repeats above-mentioned Operate three times it is ensured that unreacted hexamethylene diisocyanate cleans up in product, by the solid product 30 after cleaning DEG C it is dried under vacuum to constant weight, stand-by with DMSO dissolving (every 100mL DMSO dissolves 20g HDI-BDO-HDI chain extender) after being dried；

(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 15 weight portion L- lactides and 13 parts by weight of 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 reaction terminates, is cooled to 80 DEG C under vacuum, after adding 60ml vaccum dewatering PEG-600, after stirring, the dropwise DMSO solution of Deca HDI-BDO-HDI chain extender, after being added dropwise to complete, reacts at 80 DEG C 5h, in course of reaction, reactant viscosity can increase, and can suitably add some solvent dioxane, and the solution that reaction is completed delays Slowly pour sedimentation, sucking filtration in deionized water into, products therefrom is dried in vacuum drying oven 48h, as polylactic acid-polyurethane is common Polymers；

A9：Polylactic acid-the polyurethane copolymer of grafting piperazinedione acid and expanded PTFE granule, nanoporous silica Silicon grain mixes the compositionss obtaining, and (varicosity tetrafluoroethene granule pore size is 0.2 μm, and number-average molecular weight is 10000, micropore two Silicon oxide pore size is 1nm, and piperazinedione acid percent grafting is 2%)

Preparation method is as follows：(1) by 9 weight portion BDOs (BDO) and 68 weight portions 4,4- diphenyl methane two is different Cyanate is added in 250ml there-necked flask, is warming up to 80 DEG C of reaction 5h, after having reacted, is cooled to room temperature, product is turned Move on in beaker, add normal hexane cleaning, stir 5min with Glass rod, so that solid product is completely dispersed, sucking filtration, repeats above-mentioned Operate three times it is ensured that unreacted hexamethylene diisocyanate cleans up in product, by the solid product 30 after cleaning DEG C it is dried under vacuum to constant weight, stand-by with DMSO dissolving (every 100mL DMSO dissolves 20g HDI-BDO-HDI chain extender) after being dried；

(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 15 weight portion L- lactides and 13 parts by weight of 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 reaction terminates, thing is cooled to 80 DEG C under vacuum, after adding 60ml vaccum dewatering PEG-600, after stirring, the dropwise DMSO solution of Deca HDI-BDO-HDI chain extender, after being added dropwise to complete, reacts at 80 DEG C 5h.In course of reaction, reactant viscosity can increase, and can suitably add some solvent dioxane, and the solution that reaction is completed delays Slowly pour sedimentation, sucking filtration in deionized water into, products therefrom is dried in vacuum drying oven 48h, as polylactic acid-polyurethane is common Polymers；

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 1nm, and piperazinedione acid percent grafting is 2%)

Preparation method is as follows：(1) 9 weight portions 1,4- butanediol (BDO) are added with 68 weight portion PPDIs To in 250ml there-necked flask, it is warming up to 80 DEG C of reaction 5h, after having reacted, is cooled to room temperature, product is transferred to beaker In, 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 cleaning after 30 DEG C of vacuum of solid product It is dried to constant weight, stand-by with DMSO dissolving (every 100mL DMSO dissolves 20g HDI-BDO-HDI chain extender) after being dried；

(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 15 weight portion L- lactides and 13 parts by weight of 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.Instead, thing is cooled to 80 DEG C under vacuum, 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, reacts 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；

A11：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 2%)

Preparation method is as follows：(1) 9 weight portion diethylene glycols are added to 68 weight portion isophorone diisocyanate In 250ml there-necked 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 normal hexane cleaning, stir 5min with Glass rod, so that solid product is completely dispersed, sucking filtration, repeats aforesaid operations three times, really Protect unreacted hexamethylene diisocyanate in product to clean up, 30 DEG C of solid product after cleaning is dried under vacuum to Constant weight, stand-by with DMSO dissolving (every 100mL DMSO dissolves 20g HDI-BDO-HDI chain extender) after being dried；

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 30000, micropore Silicon dioxide aperture size is 1nm, and piperazinedione acid percent grafting is 2%, the quality of varicosity tetrafluoroethene and mesoporous silica Than for 0.5：1)

Preparation method is as follows：(1) by 9 weight portions 1,4- butanediol (BDO) and 68 weight portion hexamethylene diisocyanates It is added in 250ml 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 cleaning after 30 DEG C of vacuum of solid product It is dried to constant weight, stand-by with DMSO dissolving (every 100mL DMSO dissolves 20g HDI-BDO-HDI chain extender) after being dried；

(4) add piperazinedione acid polydactyl acid-polyurethane copolymer in there-necked flask, be warming up to 120 DEG C, solid In molten condition, add 0.05 weight portion expanded polytetrafluoroethylsealing granule, stir 0.5h, add 0.1 weight portion nanoporous silica Silicon grain, is stirred for 1h, and solid is in molten condition vacuumizing and defoaming, pours the mixture of mix homogeneously in mould into immediately, will Mould is put in 100 DEG C of baking oven and is heated 2h, raises for case temperature to 120 DEG C of recurring 2h, the demoulding, that is, obtain spherical rubber and hold Device.

A13：Polyurethane

Preparation method is as follows：(1) by 9 weight portions 1,4- butanediol (BDO) and 68 weight portion 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 turned Move on in beaker, add normal hexane cleaning, stir 5min with Glass rod, so that solid product is completely dispersed, sucking filtration, repeats above-mentioned Operate three times it is ensured that unreacted hexamethylene diisocyanate cleans up in product, by the solid product 30 after cleaning DEG C it is dried under vacuum 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.

A14：Polylactic acid-polyurethane copolymer

Preparation method is as follows：(1) by 9 weight portions 1,4- butanediol (BDO) and 68 weight portion 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 turned Move on in beaker, add normal hexane cleaning, stir 5min with Glass rod, so that solid product is completely dispersed, sucking filtration, repeats above-mentioned Operate three times it is ensured that unreacted hexamethylene diisocyanate cleans up in product, by the solid product 30 after cleaning DEG C it is dried under vacuum to constant weight, stand-by with DMSO dissolving (every 100mL DMSO dissolves 20g HDI-BDO-HDI chain extender) after being dried；

(3) add polylactic acid-polyurethane copolymer in there-necked flask, be warming up to 120 DEG C, solid is in molten condition, uses Steam mold molding obtains modified polyurethane composition.

A15：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 15 weight portion L- lactides and 13 parts by weight of caprolactone in vacuum response bottle, then plus Enter 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, 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, uses steam mold Molding obtains spherical polylactic acid.

B1:Band

C1:Band stopple

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

Embodiment 1

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

Embodiment 2

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

Embodiment 3

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

Embodiment 4

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

Embodiment 5

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

Embodiment 6

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

Embodiment 7

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

Embodiment 8

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

Embodiment 9

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

Embodiment 10

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

Embodiment 11

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

Embodiment 12

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

Comparative example 1

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

Comparative example 2

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

Comparative example 3

Combined by A15, B1, C1, obtain combination container, pack Flos Rosae Rugosae.

Flos Rosae Rugosae to above-described embodiment 1～12 and comparative example 1～3 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 in the flower arrangement device preparation method of the present invention, Spherical polylactic acid, not percent grafting piperazinedione acid modified polyurethane composition are contrasted, the flower arrangement device preparation side of the present invention The flower arrangement device that method obtains is in flower packaging, fresh-keeping, transport, have 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 preparation method of flower arrangement device is it is characterised in that comprise the steps：

Wherein, described band cervical region spherical rubber container material is modified polyurethane composition, and it includes at least polylactic acid, poly- ammonia Ester, piperazinedione acid, expanded PTFE and mesoporous silica；Band material is rubber；Band stopple material is EVA foam Or high-elastic PE.

2. the preparation method of the flower arrangement device described in claim 1 is it is characterised in that the spherical rubber container material of described band cervical region For modified polyurethane composition, its preparation method comprises the steps：

(1) pre-polymerization：Add diisocyanate and dihydroxylic alcohols by weight in reaction bulb, be warming up to 80～100 DEG C of reactions 3～ 8h, is cooled to room temperature, filters, 30～40 DEG C of dryings, obtains polyurethane prepolymer；

(2) copolymerization：Add by weight in lactide, caprolactone and catalyst vacuum response bottle, under vacuum condition, 130～150 DEG C reaction 20～30h prepares polylactic acid prepolymer, is cooled to 80 DEG C, adds polyurethane prepolymer in PEG-600 and step (1), 80 DEG C of reaction 3～6h, add deionized water to be settled, filter, be dried, obtain polylactic acid-polyurethane copolymer；

(3) modified：Solid in step (2) hydrogenperoxide steam generator of 2vt% acetum and 5wt% is dissolved, by weight Part add piperazinedione acid solution, react 3～8h, with 10wt%NaOH aqueous solution adjust pH be in neutrality after filter, be dried；

(4) it is blended：Under the conditions of in step (3), solid is warming up to 110～140 DEG C, solid sequentially adds expanded after being completely dissolved Polytetrafluoroethylgranule granule and mesoporous silica particles, after stirring, obtain modified polyurethane combination with steam mold molding Thing.

3. arrange flowers described in claim 2 device preparation method it is characterised in that the preparation side of described modified polyurethane composition Method, calculates by weight, at least includes 60～75 weight portion diisocyanate；5～12 weight portion dihydroxylic alcohols；10～20 weight portions Lactide；10～20 parts by weight of caprolactone；0.05～0.5 weight portion expanded PTFE；0.05～0.5 weight portion micropore two Silicon oxide.

4. described in claim 2 arrange flowers device preparation method it is characterised in that diisocyanate described in step (1) at least For hexamethylene diisocyanate, 4,4- methyl diphenylene diisocyanate, Toluene-2,4-diisocyanate, 4- diisocyanate, 1,5- naphthalene two are different One or more of cyanate, PPDI, isophorone diisocyanate.

5. described in claim 2 arrange flowers device preparation method it is characterised in that dihydroxylic alcohols described in step (1) are at least 1, One or more in 4- butanediol, diethylene glycol, Polyethylene Glycol, polyester diol, polyether Glycols.

6. described in claim 2 arrange flowers device preparation method it is characterised in that be modified as described in step (3) polylactic acid- Grafting piperazinedione acid on polyurethane copolymer, its percent grafting is 1～3%.

7. the preparation method of the flower arrangement device described in claim 2 is it is characterised in that described expanded polytetrafluoroethylsealing and micropore two The mass ratio of silicon oxide is (0.5～2)：1.

8. the preparation method of the flower arrangement device described in claim 1 is it is characterised in that the number of described expanded polytetrafluoroethylsealing is divided equally Son is measured as 5000～30000.

9. the preparation method of the flower arrangement device described in claim 1 is it is characterised in that the aperture of described expanded polytetrafluoroethylsealing is big Little is 0.1～1.5 μm.

10. the preparation method of the flower arrangement device described in claim 1 is it is characterised in that the aperture of described mesoporous silica is big Little for 1nm～2nm.