CN107446343B - A kind of micro- balloon polymer elastomeric material of degradable antifouling thermoplasticity and its preparation - Google Patents

A kind of micro- balloon polymer elastomeric material of degradable antifouling thermoplasticity and its preparation Download PDF

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Publication number
CN107446343B
CN107446343B CN201710660143.9A CN201710660143A CN107446343B CN 107446343 B CN107446343 B CN 107446343B CN 201710660143 A CN201710660143 A CN 201710660143A CN 107446343 B CN107446343 B CN 107446343B
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polymer
pressure
melt
degradable
process water
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CN107446343A (en
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陈乔健
郭杨龙
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Nantong Deyi New Material Co Ltd
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Nantong Deyi New Material Co Ltd
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Priority to CN201811081676.2A priority patent/CN109320951B/en
Publication of CN107446343A publication Critical patent/CN107446343A/en
Priority to PCT/CN2018/088920 priority patent/WO2019024588A1/en
Priority to PCT/CN2018/098027 priority patent/WO2019024869A1/en
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Abstract

The present invention relates to a kind of degradable antifouling micro- balloon polymer elastomeric materials of thermoplasticity, component including following weight percent content: polymer raw material 88~98%, nucleating agent 0.05~0.5%, foaming agent 0.4~2%, the organic perfluorinated material 0.1~10% of environment-friendly degradable；Preparation method specifically: (1) feed polymer raw material, nucleating agent and the organic perfluorinated material of environment-friendly degradable from Bitruder front end feed opening, foaming agent is fed from Bitruder middle section feed opening, after making each raw material hot melt mixing sufficiently, it enters back into static mixer further to homogenize, then again through Melt Pump pressure control and quantitative conveying；(2) pelletizing of underwater cutpellet room is entered by die head by the hot melt that melt pumps out, and separation is taken out of by process water, form purpose product after gained particle screen selecting is dry.Compared with prior art, the present invention can effectively realize the antifouling of material, bear dirty, oil resistant, anti-contamination, beautiful, the performances such as good sense of touch, especially suitable for the application in the fields such as footwear material and food packaging.

Description

A kind of micro- balloon polymer elastomeric material of degradable antifouling thermoplasticity and its preparation
Technical field
The present invention relates to macromolecule material preparation areas, polymerize more particularly, to a kind of degradable antifouling micro- air bag of thermoplasticity Object elastomeric material and its preparation.
Background technique
Thermoplastic polymer elastic material manufactures production and live facility used, equipment, tool and consumables extensively, with The development of society also becomes more and more urgent to environmental protection, energy conservation, the requirement of lower consumption etc., the demand of material lightweight.Thermoplastic Property polymeric elastic material also largely start it is light-weighted experiment and verify and continue to promote and apply.But thermoplastic expanded polymer When elastomer directly applies to the direct consumer goods, when without being modified and is special, thermoplastic expanded conducting polymer rate is generally big 11 powers or more in 10 lead to easy to produce static electricity and Electrostatic Absorption, make material be difficult solve outer surface it is dry and astringent, easily it is dirty The problems such as.Such as the foaming polyurethanes elastomer particle for sole, consumer after a period of use, sole surface can be stained with Contaminate a large amount of dusts, surface also can dirty as time went on and not easy cleaning.Since domestic material lightweight has just started, institute With the antifouling modification to foamed thermoplastic polymer elastomer there is not yet research report and patent and report.
It still needs to possess good physical property after the foaming and extruding of thermoplastic polymer elastic material, in addition to requiring to extruding Material structure and material abscess etc., which are designed, afterwards outer also needs to be designed on anti-pollution function antistatic.But it is limited by material Expect structural property itself and processing technology, the understanding of foam theory and generating material are easily dirty, easily the understanding of dirt condition, lead to state The material of the interior thermoplastic polymer elastic material to extruding does not temporarily control effectively and considers.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of degradable antifouling heat The micro- balloon polymer elastomeric material of plasticity and its preparation.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of degradable antifouling micro- balloon polymer elastomeric material of thermoplasticity, the group including following weight percent content Point: polymer raw material 88-98%, nucleating agent 0.05~0.5%, foaming agent 0.4~2%, the organic perfluorinated material of environment-friendly degradable 0.1~10%.
As preferred embodiment, the support frame polymer material be high molecular weight, high rigidity, it is highly crystalline or Highly polar polymer material, the pressure-resistant low resilience polymer material are low point corresponding with support frame polymer material Sub- amount, low crystallizes to amorphous state, low polarity to polar polymeric material at soft.
As above-mentioned preferred embodiment it is further preferred that the support frame polymer material is high-molecular-weight poly ammonia Ester, corresponding pressure resistance low resilience polymer material is low molecular weight polyurethane；
Or the support frame polymer material is that high rigidity thermoplastic polymer elastomer (can be according to the actual situation Select such as TPU, TPE or rubber), corresponding pressure resistance low resilience polymer material is soft thermoplastic polymer elasticity Body；
Or the support frame polymer material is polyamide or polyester, corresponding pressure resistance low resilience polymer material For thermoplastic polyurethane.
Still more preferably as above-mentioned further preferred embodiment, the molecular weight M of the high molecular weight polyurethanew It is 8 × 104~5 × 105, the molecular weight M of low molecular weight polyurethanewIt is 2 × 104~2.5 × 105；
The shore hardness of high rigidity thermoplastic polymer elastomer is 80A~75D soft thermoplastic polymer elastomer Shore hardness be 30~85A；
Polyester or polyamide are respectively modified low-melting point polyester or modified low melting point polyamide, and control support frame polymerization The fusing point difference of object material and pressure resistance rebound polymer material is in 20 DEG C.It is furthermore preferred that modified low-melting point polyester can choose as Modified PET, PTT, PBT etc., modified low melting point polyamide can such as low melting point modified PA6, PA6I, PA11, PA12, PA9.
The organic perfluorinated material of environment-friendly degradable is the PM-870 function selected from 3M company as a preferred technical solution, It can sexupara grain.
The nucleating agent is selected from carbon nanotube, silica, talcum powder, modified carbonic acid as a preferred technical solution, At least one of calcium, carbon black or tetrafluoroethene pulvis；
The foaming agent is selected from CO2、N2, normal butane, at least one of pentane or isopentane.
The preparation method of the degradable micro- balloon polymer elastomeric material of antifouling thermoplasticity, preferably the following steps are included:
(1) polymer raw material, nucleating agent and the organic perfluorinated material of environment-friendly degradable are fed from Bitruder front end Mouth feeding, foaming agent are fed from Bitruder middle section feed opening, after keeping each raw material hot melt mixing abundant, are entered back into static mixed Clutch further homogenizes, then again through Melt Pump pressure control and quantitative conveying；
(2) pelletizing of underwater cutpellet room is entered by die head by the hot melt that melt pumps out, and separation is taken out of by process water, Purpose product is formed after gained particle screen selecting is dry.
As above-mentioned preferred technical solution it is further preferred that the temperature of Bitruder is 160~300 in step (1) DEG C, double screw extruder draw ratio is 32-56；
Temperature in static mixer is set as 120-260 DEG C, and the inlet pressure of Melt Pump is 50-200bar, and is controlled The difference of the pressure of process water is 70-120bar in the hot melt pressure squeezed out through die head and underwater cutpellet room.
As above-mentioned preferred technical solution it is further preferred that the technique coolant-temperature gage in step (2) in underwater cutpellet room is 10- 90 DEG C, pressure 4-20bar；
When pelletizing is taken out of by process water, the multistage discharge expansion process water pipeline reduced step by step through excess pressure is conveyed.
As the further preferred of above-mentioned further preferred embodiment, multistage discharge expansion process water pipeline in step (2) For multi-stage process water pipeline, wherein the water pressure of first order technique water pipeline is kept and the technique hydraulic pressure into underwater cutpellet room Power is consistent.Still more preferably, multistage discharge expansion process water pipeline is level Four technique water pipeline in step (2), wherein the The hydraulic pressure of level-one technique water pipeline is 4-20bar, and the hydraulic pressure of second level technique water pipeline is 3-10bar, third level technique water pipe The hydraulic pressure of line is 2-6bar, and the hydraulic pressure of fourth stage technique water pipeline is 1-4bar.It is further preferred that in above-mentioned preparation process, Bitruder runs Bitruder in 50~900rpm revolving speed, the barrel setting of extruding machine 160~300 DEG C of temperature ensure that thermoplastic polymer can be heated sufficiently, and polymer raw material, nucleating agent and environment-friendly degradable are organic complete Fluorine material is fed from front end screw rod feed opening, and foaming agent is fed from the screw rod feed opening in middle section.After mixing extruding machine heat with And under the shearing force of screw rod, each material is melted by heat and sufficiently enters static mixer afterwards in screw mixes, and melt is in static mixing The deep step of progress, which is homogenized and cooled down, in device ensures melt temperature between 120~260 DEG C, and can require according to finished product physical property can Control.It is acted on by the pressure control of Melt Pump and quantitative conveying, the inlet pressure for setting Melt Pump controls between 50~200bar squeezes Melt pressure is stablized in molding machine spiral shell thorax, makes sufficiently mixed in controllable hyperbaric environment in the hot melt of mixed foaming agent and nucleating agent It closes and is homogenized.By Melt Pump pressure control and quantitative conveying function by the push-in extruder die of hot high pressure Melt Stability, die head is Porous AND DEWATERING FOR ORIFICE STRUCTURE, inside ensure that hot melt physical efficiency stabilization passes through die head containing facility is evenly heated.It is sent out by Melt Pump high pressure Hot melt by each hole of die head, beans granular solid matter, underwater cutpellet by high-speed rotating grain-cutter are cut into pelletizing room under water The grain-cutter of room really cuts hot melt under water.10~90 DEG C of process water generates 6 under the action of technique water pump~ The pressure of 20bar enters the such high pressure hot melt in underwater cutpellet room in high-pressure process water by the process water water inlet pipe of pelletizing water chamber Under be cooled rapidly and be cut by grain-cutter granular.Since there are pressure differences between high pressure hot melt and high-pressure process water, and this Kind pressure difference can be adjusted by the inlet pressure and frequency conversion technique water-aspirator pressure of Melt Pump, so that being cut into grain in entire technique The polymer initial bubble rate and multiplying power of shape are controllable and stablize.Because the cooling time of the granular polymer just cut is short and not Material crystalline speed is widely different in same formula, has been specifically designed multistage discharge expansion process water pipeline in the art, benefit With the exocuticle of granular polymer, residence time longer intensity is higher in process water, the higher principle of pressure-bearing condition, first The hydraulic pressure of 4-20bar is still maintained in grade technique water pipeline, granular melt portion is cooling and under the conditions of existing for the pressure difference at this time Preliminary expansion.The becoming larger and shortening hydraulic pressure is down to 3~10bar by pipeline diameter in the technique water pipeline of the second level, at this time It also can reflation after the granular further cooled external intensity of melt rises but pressure difference becomes larger.Lead in third level technique water pipeline Becoming larger and shorten and dropping low pipe resistance hydraulic pressure is down to 2~6bar for pipeline diameter is crossed, granular melt cools down again at this time, and outer surface is strong Degree continue rise but pressure difference become larger after also reexpand but since grain crystalline is soon completed thus expansion rate be down to it is very low.? In fourth stage technique water pipeline or low pipe resistance is dropped by pipeline diameter and length adjustment is down to 1~4bar for hydraulic pressure, at this time Granular melt continues to cool down, and appearance surface intensity is further up but pressure difference is still after becoming larger can yet expand but because of cooling time Enough particle exocuticle intensity also complete to keep the sizing of particle outer diameter firm very high and particle substantially by crystallization.After granular extruding Polymer and water enter in centrifugal separator jointly, and water and the separation of the particle of extruding, the particle after expansion enter vibration herein Dynamic sieve enters after-treatment system, and process water is flowed out from centrifugal separator enters technique water tank.Repeatedly, keep technique continuous It carries out.
Heavy polymer involved in the present invention and low-molecular weight polymer, high durometer polymeric and soft are poly- It closes object, high crystallinity polymer and crystallizes to amorphous state polymer, highly polar polymer and rudimentary property or polar polymeric with low It Deng high molecular weight and the low molecular weight etc. in combination is distinguished by the different two kinds of polymer material comparison of physical property, i.e., The two kinds of polymer raw material of different physical property, molecular weight is higher to be defined as heavy polymer, and molecular weight is lower then fixed Justice is low-molecular weight polymer, and similarly, high rigidity and soft etc. are also analogy definition.It is furthermore preferred that high molecular weight polymerize The molecular weight of object is at least twice above than low-molecular weight polymer；The hardness of high durometer polymeric should be than soft polymer Poor 10A or more.
Preferably, rise rebound effect pressure resistance rebound polymer material should select elastomer quasi polymer material, as TPU, Rubber, TPE etc., the support frame polymer material to play a supportive role can be elastomer quasi polymer material, also can choose Non-elastomeric material, such as PET, PTT.
In the present invention unless otherwise noted, each raw material and the processing step being related to can use any those skilled in the art Raw material or technology known to member.As thermoplastic polyurethane can be using by directlying adopt commercial product or according to known work Skill technology oneself preparation.It is furthermore preferred that thermoplastic polyurethane can need to select such as polyether thermoplastic polyurethane according to product Or polyester-type thermoplastic polyurethane.
The present invention in the preparation, passes through the micro- gas in inside for designing and controlling swelling granular with ratio optimization to raw material selection Inside capsule size, size, density and swelling granular and epidermis opens the form, size and density of abscess, meanwhile, pass through hot melt Melt pressure of the polymer melt in Bitruder spiral shell thorax and the pressure of extruding machine controls bubble swelling of nucleus out, finally, The method of pressure is sustained by melt pressure and process water pressure difference and process water to control foam solidifying and setting.
Preferably, the present invention is poly- by design heavy polymer and low-molecular weight polymer, high rigidity on raw material It closes object and soft polymer, high crystallinity polymer and crystallizes to amorphous state polymer, highly polar polymer and rudimentary property with low Or polar polymeric is respectively combined, and foaming agent is added after hot melt then is blended, then after controllable bulking process, utilizes hair The difference of foaming capacity of the infusion in different physical property polymer raw materials obtains atomic closed airbag structure support component and opening Foam component collectively constitutes the netted composite puffed material of interpenetrating air passage structure of winding.Wherein, by high molecular weight or high rigidity or Formed under the action of nucleating agent countless 0.01~20 microns of highly crystalline or highly polar polymer material and foaming agent it is small Closed air bag, and support component is served as in bulking meterial by these small closed air bags, and low molecule or soft or low knot Brilliant or low polarity/polar polymeric is then formed with foaming agent superfine micro- open cells (non-closed pore), and with part extruding group Pressure-resistant low resilience component is synthesized, forms the air flue for winding closed micro- air bag, and gas in these open cells in bulking meterial It is partially connected between road and extends to bulking meterial particle surface.In this way, when bulking meterial is squeezed, in support component Small closed pneumatopyle, which is squeezed, plays support effect, and the air in open cells in pressure-resistant low resilience component is then squeezed rapidly Extrusion is gone, and the good extruding soft feeling of bulking meterial and better stability of strutting system are assigned；And when extruding force disappears, it is micro- Small closed air bag then supports bulking meterial to reset, and outside air is inhaled into open cells therewith.Entire material can integrally obtain Preferably buffering feedback.
In addition, the present invention can also utilize infiltration of the different foaming agents in different polymer materials during the preparation process Saturating rate difference, the difference of different materials melt strength in different pressure differences and caused by melt crystallization speed, different polymer are swollen Physical property changes the difference retained with transitivity after change, to control micro- air bag size and how many, Yi Jikai in the material after extruding How much mouthful cell size, shape and achieve the purpose that meet different downstream uses and customer requirement to adjust the physical property of material.
The present invention during the preparation process, when needing to obtain large opening or open cells ratio deficiency, in Constant process water At a temperature of, increase melt booster pump inlet pressure, to increase die entrance pressure indirectly, and is released by the acceleration of technique water pressure Pressure.When needing to reduce aperture or open cells ratio, under Constant process coolant-temperature gage, reduce melt booster pump inlet pressure, Reduce die entrance pressure indirectly, and passes through process water pressure relieving discharge.
Compared with prior art, the invention has the following advantages that
(1) present invention is designed by the composition of raw materials to thermoplastic polymer elastic material, is made to have height in itself and be led The material surface polarity of electric rate becomes smaller, and then the body for improving material is grease proofing, antifouling, waterproof performance, meanwhile, so that sense of touch rises. In the present invention, by modified environment-friendly degradable type perfluorinated material, the dispersion when polymer material synthesizes is added for selection, makes the environmental protection Degradable perfluorinated material can be well dispersed in material system, and realize that reduction is led by mutually separating in the subsequent process Electric rate and polarity are uniformly distributed.Make environment-friendly degradable type perfluorinated material be capable of forming ion by subsequent processing and bulking process to become To reduction conductivity and surface polarity, grease proofing so as to improve the antifouling of expanded thermoplastic surface of polymer material, waterproof and touching Sense.
(2) thermoplastic, polymeric materials produced by the present invention can be widely used in the fields such as footwear material and food packaging.
(3) compared to the general bulking meterial using closed micropore made of single physical property polymer raw materials, the present invention Polymer raw material is formed using two kinds of different physical property polymer, forming it during puffing foaming has suitable micro- air bag The open cells of structure and appropriateness form winding network air flue interpenetrating structure, in this way, micro- airbag structure can provide very for material Good physical property, such as intensity, elasticity modulus and screen resilience, and the energy-absorbing energy storage of material then can be improved in open cells structure Property, contact sense and comfort.
(4) by adjustment to formula and adjustment of technology can effectively adjust micro- air bag and open cells structure, Opening form and density, size etc., and micro- air bag in material can be effectively controlled and account for 20~99.5% of volume or so, opening Abscess accounts for 0.5~80% of material volume or so.
(5) it can be cut by the back pressure of the hot melt in control Bitruder and under water in preparation process of the invention The back pressure of grain room stablizes the speed and multiplying power of discharge extruding, reaches the requirement for being precisely controlled material expansion multiplying power.
(6) using the process of multistage gradually discharge, wanting for brokenly bubble rate in different polymer expansion processes can flexibly be controlled It asks to reach the suitable composite puffed structural material of manufacture.
(7) polymer elastomer material prepared by the present invention is suitable for article of footwear, packaging, damping, heat preservation, seat, race The foamed materials application field such as road, solid tyre.
Detailed description of the invention
Fig. 1 is process flow chart of the invention；
Fig. 2 is the SEM photograph of material internal made from the embodiment of the present invention 1；
Fig. 3 is the SEM photograph of material surface made from the embodiment of the present invention 1；
In figure, 1- motor, 2- Bitruder, 3- spout one, 4- spout two, 5- static mixer, 6- melt Pump, 7- die head, 8- underwater cutpellet room, 9- process water inlet tube, 10- process water level-one discharge pipe, 11- process water second level discharge Pipe, 12- process water three-level discharge pipe, 13- process water level Four discharge pipe, 14- centrifugal separator, 15- vibrating screen, 16- technique Water pump component.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
It is necessarily pointed out that following implementation and embodiment are served only for, the invention will be further described, no It can be interpreted as limiting the scope of the invention, professional and technical personnel in the field makes according to the content of aforementioned present invention Some nonessential modifications and adaptations, still fall within protection scope of the present invention.
In addition, if without other explanations, it is raw materials used to be all commercially available.
The detailed description for preferred implementation method of the invention below of participating in the election of and including embodiment this hair can be more easily to understand Bright content.Unless otherwise defined, all technologies used herein and scientific term have common with fields of the present invention The normally understood identical meaning of technical staff.When there is a conflict, the definition in this specification shall prevail.
As used herein term " by ... preparation " it is synonymous with "comprising".Term "comprising" used herein, " comprising ", " having ", " containing " or its any other deformation, it is intended that cover non-exclusionism includes.For example, the combination comprising listed elements Object, step, method, product or device are not necessarily limited to those elements, but may include not expressly listed other elements or Such composition, step, method, product or the intrinsic element of device.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit When the Range Representation that choosing value limits, this should be understood as specifically disclosing by any range limit or preferred value and any range Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open When range " 1 to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to 5 ", " 1 to 3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise the range is intended to include its end Value and all integers and score in the range.
Approximate term in specification and claims is used to modify quantity, and it is specific to indicate that the present invention is not limited to this Quantity further includes the acceptable modified part without will lead to the change of dependency basis this function close with the quantity.Phase It answers, modifies a numerical value with " about ", " about " etc., mean that the present invention is not limited to the exact numericals.In some examples, approximate Term likely corresponds to the precision of the instrument of measurement numerical value.In present specification and claims, range limits can be with Combination and/or exchange, these ranges if not stated otherwise include all subranges contained therebetween.
In addition, indefinite article "an" before element of the present invention or component and "one" quantitative requirement to element or component (i.e. frequency of occurrence) unrestriction.Therefore "one" or "an" should be read as including one or at least one, and odd number The element or component of form also include plural form, unless the obvious purport of the quantity refers to singular.
" polymer " means polymerizable compound prepared by the monomer by the identical or different type of polymerization.Generic term " polymer " includes term " homopolymer ", " copolymer ", " terpolymer " and " copolymer ".
A kind of degradable antifouling micro- balloon polymer elastomeric material of thermoplasticity, the group including following weight percent content Point: polymer raw material 88-98%, nucleating agent 0.05~0.5%, foaming agent 0.4~2%, the organic perfluorinated material of environment-friendly degradable 0.1~10%.
As a kind of perferred technical scheme, the polymer raw material is by support frame polymer material (60-95%) It is composed with pressure-resistant low resilience polymer material (3-38%), wherein the support frame polymer material is macromolecule Amount, high rigidity, highly crystalline or highly polar polymer material, the pressure-resistant low resilience polymer material are to polymerize with support frame Object material corresponding low molecular weight, low crystallizes to amorphous state, low polarity/polar polymeric material at soft.
As above-mentioned preferred embodiment it is further preferred that the support frame polymer material is high-molecular-weight poly ammonia Ester, corresponding pressure resistance low resilience polymer material is low molecular weight polyurethane；
Or the support frame polymer material is that high rigidity thermoplastic polymer elastomer (can be according to the actual situation Select such as TPU, TPE or rubber), corresponding pressure resistance low resilience polymer material is soft thermoplastic polymer elasticity Body；
Or the support frame polymer material is polyamide or polyester, corresponding pressure resistance low resilience polymer material For thermoplastic polyurethane.
Still more preferably as above-mentioned further preferred embodiment, the molecular weight M of the high molecular weight polyurethanew It is 8 × 104~5 × 105, the molecular weight M of low molecular weight polyurethanewIt is 2 × 104~2.5 × 105；
The shore hardness of high rigidity thermoplastic polymer elastomer is 80A~75D soft thermoplastic polymer elastomer Shore hardness be 30~85A；
Polyester or polyamide are respectively modified low-melting point polyester or modified low melting point polyamide, and control support frame polymerization The fusing point difference of object material and pressure resistance rebound polymer material is in 20 DEG C.It is furthermore preferred that modified low-melting point polyester can choose as Modified PET, PTT, PBT etc., modified low melting point polyamide can such as low melting point modified PA6, PA6I, PA11, PA12, PA9.
The organic perfluorinated material of environment-friendly degradable is selected from the PM-870 function of 3M company as a preferred technical solution, Sexupara grain.
The nucleating agent is selected from carbon nanotube, silica, talcum powder, modified carbonic acid as a preferred technical solution, At least one of calcium, carbon black or tetrafluoroethene pulvis；
The foaming agent is selected from CO2、N2, normal butane, at least one of pentane or isopentane.
The preparation method of the degradable micro- balloon polymer elastomeric material of antifouling thermoplasticity, preferably the following steps are included:
(1) polymer raw material, nucleating agent and the organic perfluorinated material of environment-friendly degradable are fed from Bitruder front end Mouth feeding, foaming agent are fed from Bitruder middle section feed opening, after keeping each raw material hot melt mixing abundant, are entered back into static mixed Clutch further homogenizes, then again through Melt Pump pressure control and quantitative conveying；
(2) pelletizing of underwater cutpellet room is entered by die head by the hot melt that melt pumps out, and separation is taken out of by process water, Purpose product is formed after gained particle screen selecting is dry.
As above-mentioned preferred technical solution it is further preferred that the temperature of Bitruder is 160~300 in step (1) DEG C, double screw extruder draw ratio is 32-56；
Temperature in static mixer is set as 120-260 DEG C, and the inlet pressure of Melt Pump meets: the heat squeezed out through die head The difference of the pressure of process water is 70-120bar in melt pressure and underwater cutpellet room.
As above-mentioned preferred technical solution it is further preferred that the technique coolant-temperature gage in step (2) in underwater cutpellet room is 10- 90 DEG C, pressure 4-20bar；
When pelletizing is taken out of by process water, the multistage discharge expansion process water pipeline reduced step by step through excess pressure is conveyed.
As the further preferred of above-mentioned preferred technical solution, multistage discharge expansion process water pipeline in step (2) For level Four technique water pipeline, wherein the hydraulic pressure of first order technique water pipeline is 4-20bar, the hydraulic pressure of second level technique water pipeline For 3-10bar, the hydraulic pressure of third level technique water pipeline is 2-6bar, and the hydraulic pressure of fourth stage technique water pipeline is 1-4bar.
It is furthermore preferred that the visible attached drawing 1 of the detailed description of above-mentioned preparation process, Bitruder 2 is under the driving of motor 1 With the operation of 50~900rpm revolving speed, 160~300 DEG C of barrel set temperature of Bitruder 2 ensure thermoplastic polymer energy Sufficiently hot melt, polymer raw material and nucleating agent are fed from the spout 1 of front end, and foaming agent is fed from the spout 24 in middle section. After mixing under the shearing force of heating and screw rod, each raw material is melted by heat and sufficiently enters static mixer 5 afterwards in screw mixes, Melt, which is homogenized and cooled down in the deep step of progress in static mixer 5, ensures that melt temperature between 120~280 DEG C, specifically may be used It is required according to finished product physical property controllable.It is acted on by the pressure control of Melt Pump 6 (gear pump etc. can be used) and quantitative conveying, sets melt The inlet pressure of pump 6 controls melt pressure in 2 spiral shell thorax of Bitruder and stablizes, make mixed foaming between 50~200bar It is sufficiently mixed and is homogenized in controllable hyperbaric environment in the hot melt of agent and nucleating agent.By 6 pressure control of Melt Pump and quantify defeated Send function by the die head 7 of the push-in extruding machine of hot high pressure Melt Stability, die head 7 is porous AND DEWATERING FOR ORIFICE STRUCTURE, internal containing uniform Heating facility ensures to heat physical efficiency and stablizes through die head 7.The hot melt sent out by 6 high pressure of Melt Pump passes through each hole of die head 7 Beans granular solid matter is cut by high-speed rotating grain-cutter in pelletizing room 8 under water, and the grain-cutter of underwater cutpellet room 8 is really under water Cut hot melt.10~90 DEG C of process water generates 4 under the action of technique water pump component 16 (comprising water pump and water tank etc.)~ The pressure of 15bar, and underwater cutpellet room 8 is entered by process water water inlet pipe 9.The high pressure hot melt squeezed out in this way from die head 7 It is cooled rapidly and is cut by grain-cutter granular under the process water of high pressure.Due to being deposited between high pressure hot melt and high-pressure process water In pressure difference, and this pressure difference can be adjusted by the inlet pressure of Melt Pump 6 and the discharge pressure of technique water pump component 16, So that it is controllable and stable to be cut into granular polymer initial bubble rate and multiplying power in entire technique.Because that has just cut is granular The cooling time of polymer is short and different formulations in material crystalline speed it is widely different, be specifically designed multistage in the art Discharge expansion process water pipeline (preferred level Four herein), using the exocuticle of granular polymer, the residence time is longer in process water Intensity is higher, the higher principle of pressure-bearing condition, still ties up in first order technique water pipeline (i.e. process water level-one discharge pipe 10) The hydraulic pressure of 4~15bar is held, granular melt portion is cooling at this time and existing for pressure difference under the conditions of tentatively expands.In second level work Becoming larger and shortening hydraulic pressure is down to 3~10bar by pipeline diameter in skill water pipeline (i.e. process water second level discharge pipe 11), this When the further cooled external intensity of granular melt rise but pressure difference become larger after also can reflation.In third level technique water pipeline Becoming larger and shortening and drop low pipe resistance hydraulic pressure is down to 2~6bar by pipeline diameter in (i.e. process water three-level discharge pipe 12), this When granular melt cool down again, also reexpand after appearance surface intensity continues to rise but pressure difference becomes larger but due to grain crystalline soon Complete thus expansion rate be down to it is very low.Still pass through pipe in fourth stage technique water pipeline (i.e. process water level Four discharge pipe 13) Linear diameter and length adjustment are down to 1~4bar to drop low pipe resistance for hydraulic pressure, and granular melt continues to cool down at this time, appearance surface intensity into One step rise but pressure difference can yet be expanded still after becoming larger but because enough particle exocuticle intensity cooling time it is very high and Particle also complete to keep the sizing of particle outer diameter firm substantially by crystallization.Polymer after granular extruding is separated into centrifugal jointly with water In machine 14, particle product is separated after water and extruding herein, and the particle after expansion enters vibrating screen 15 and enters after-treatment system simultaneously The output of extruding finished product is generated, process water is flowed out from centrifugal separator 14 enters technique water pump component 16.Repeatedly, make work Skill is carried out continuously.
In addition it should be pointed out that, disclosed above is only a basic components of the invention, on basis disclosed by the invention On the basis of formula, those skilled in the art can add remaining conventional auxiliary agent thereto according to actual needs, such as add anti- The anti-aging property of the raising product such as oxidant and age resister.
In following each embodiments, used polyether thermoplastic polyurethane derives from Baeyer, Hensel Mai Deng producer；It is adopted Polyester-type thermoplastic polyurethane derives from Baeyer, Hensel Mai Deng producer；Used modified low-melting point polyester PET is derived from Kingsoft petrochemical industry etc.；Used modified low melting point polyamide derives from Du Pont, Ying Chuandeng company；Used PBT is from gold The companies such as mountain petrochemical industry.
Embodiment 1
Thermoplasticity of the invention is prepared according to following composition of raw materials and process conditions according to the above-mentioned process flow such as Fig. 1 Micro- balloon polymer elastomeric material:
Wherein, molecular weight MwIn the polyether thermoplastic polyurethane of 150K~300K (K herein indicates unit thousand), it is added Ratio 75% (weight percent, similarly hereinafter), molecular weight MwIn the polyether thermoplastic polyurethane of 50K~100K, additional proportion 20%, The additional amount of the organic perfluorinated material of environment-friendly degradable is 2.5%, foaming agent CO2, additional amount 2%, nucleating agent is calcium carbonate, is added Entering amount is 0.5%.Bitruder draw ratio L/D=40,160-220 DEG C of screw rod heating temperature, static mixer temperature 140-180 DEG C, melt pump inlet pressure 100-150bar, technique water pressure 12bar or so has just enter into the work in underwater cutpellet room Skill coolant-temperature gage is 30 DEG C, the control discharge pressure difference (pressure of the process water i.e. in the high pressure hot melt of die head exit and underwater cutpellet room Power is poor) 100-150bar.In multistage discharge expansion process water pipeline, the hydraulic pressure control in first order technique water pipeline is 12bar Or so, the hydraulic pressure control in the technique water pipeline of the second level is 8bar or so, and the hydraulic pressure in third level technique water pipeline is 5bar left The right side, the hydraulic pressure control in fourth stage technique water pipeline are 2bar or so.
The SEM picture of product particle is as shown in Figures 2 and 3, it is recognised that there is apparent micro- air bag inside material granule The winding network air flue interpenetrating structure that structure and open cells are formed, and partial airway interpenetrating structure also extends to material granule table Face.Meanwhile product is dripped after test, waterproof and oilproof test reaches 5 grades, and watering test is 90 points of (Japanese Industrial Standards JIS)。
Embodiment 2
Thermoplasticity of the invention is prepared according to following composition of raw materials and process conditions according to the above-mentioned process flow such as Fig. 1 Micro- balloon polymer elastomeric material:
Wherein, molecular weight MwIn the polyether thermoplastic polyurethane of 300K~500K, 70% (weight percent of additional proportion Number, similarly hereinafter), molecular weight MwIn the polyether thermoplastic polyurethane of 150K~250K, additional proportion 18.1%, environment-friendly degradable is organic The additional amount of perfluorinated material is 10%, foaming agent N2, additional amount 1.4%, nucleating agent is carbon black, additional amount 0.5%.Double spiral shells Bar extruding machine draw ratio L/D=56,160-220 DEG C of screw rod heating temperature, 140-180 DEG C of static mixer temperature, melt is pumped into Mouth pressure 100-150bar, technique water pressure 6bar or so, the technique coolant-temperature gage control for having just enter into underwater cutpellet room is 60 DEG C, control Discharge pressure difference (pressure difference of the process water i.e. in the high pressure hot melt of die head exit and underwater cutpellet room) 90-150bar processed.It is more In grade discharge expansion process water pipeline, the hydraulic pressure control in first order technique water pipeline is 6bar or so, second level technique water pipe Hydraulic pressure control in line is 5bar or so, and the hydraulic pressure in third level technique water pipeline is 3bar or so, fourth stage technique water pipeline In hydraulic pressure control be 1bar or so.
Product is dripped after test, and waterproof and oilproof test reaches 5 grades, and watering test is 90 points of (Japanese Industrial Standards JIS)。
Embodiment 3
Thermoplasticity of the invention is prepared according to following composition of raw materials and process conditions according to the above-mentioned process flow such as Fig. 1 Micro- balloon polymer elastomeric material:
Wherein, molecular weight MwIn the polyether thermoplastic polyurethane of 80K~120K, additional proportion 90% (weight percent, Similarly hereinafter), molecular weight MwIn the polyether thermoplastic polyurethane of 20K~50K, additional proportion 9%, the organic perfluorinated material of environment-friendly degradable Additional amount be 0.1%, foaming agent N2, additional amount 0.4%, nucleating agent is talcum powder and modified calcium carbonate 1:1 in mass ratio Mixture, additional amount 0.5%.Bitruder draw ratio L/D=38,160-220 DEG C of screw rod heating temperature, static state are mixed 130-170 DEG C of clutch temperature, melt pump inlet pressure 100-150bar, technique water pressure 15bar or so have just enter into underwater cutpellet The technique coolant-temperature gage of room is 40 DEG C or so, and control discharge pressure difference is (i.e. in the high pressure hot melt of die head exit and underwater cutpellet room The pressure difference of process water) 90-140bar.Water pressure controlled in multistage discharge expansion process water pipeline, in first order technique water pipeline It is made as 15bar or so, the hydraulic pressure control in the technique water pipeline of the second level is 10bar or so, the water in third level technique water pipeline Pressure is 6bar or so, and the hydraulic pressure control in fourth stage technique water pipeline is 4bar or so.
Product is dripped after test, and waterproof and oilproof test reaches 5 grades, and watering test is 90 points of (Japanese Industrial Standards JIS)。
Embodiment 4
Thermoplasticity of the invention is prepared according to following composition of raw materials and process conditions according to the above-mentioned process flow such as Fig. 1 Micro- balloon polymer elastomeric material:
Wherein, molecular weight MwIn the polyether thermoplastic polyurethane of 80K~120K, additional proportion 65% (weight percent, Similarly hereinafter), molecular weight MwIn the polyether thermoplastic polyurethane of 20K~50K, additional proportion 25%, the organic perfluor material of environment-friendly degradable The additional amount of material is 8%, foaming agent N2, additional amount 1.8%, nucleating agent is carbon nanotube, additional amount 0.2%.Twin-screw Extruding machine draw ratio L/D=52,160-220 DEG C of screw rod heating temperature, 140-180 DEG C of static mixer temperature, melt pump intake Pressure 100-150bar, technique water pressure 10bar or so, the technique coolant-temperature gage for having just enter into underwater cutpellet room is 30 DEG C or so, control Discharge pressure difference (pressure difference of the process water i.e. in the high pressure hot melt of die head exit and underwater cutpellet room) 90-150bar processed.It is more In grade discharge expansion process water pipeline, the hydraulic pressure control in first order technique water pipeline is 10bar or so, second level technique water pipe Hydraulic pressure control in line is 7bar or so, and the hydraulic pressure in third level technique water pipeline is 4bar or so, fourth stage technique water pipeline In hydraulic pressure control be 2bar or so.
Product is dripped after test, and waterproof and oilproof test reaches 5 grades, and watering test is 90 points of (Japanese Industrial Standards JIS)。
Embodiment 5
Thermoplasticity of the invention is prepared according to following composition of raw materials and process conditions according to the above-mentioned process flow such as Fig. 1 Micro- balloon polymer elastomeric material:
Wherein, molecular weight MwIn the poly- ammonia of polyether thermoplastic of 120K~180K (K herein indicates unit thousand, PLSCONFM) Ester, additional proportion 95% (weight percent, similarly hereinafter), molecular weight MwIn the polyether thermoplastic polyurethane of 20K~50K, ratio is added Example 3%, the additional amount of the organic perfluorinated material of environment-friendly degradable are 1%, and foaming agent is the CO that volume ratio 1:1 is added2With N2, it is added Amount 0.8%, nucleating agent are calcium carbonate and the tetrafluoroethene pulvis mixture of 1:1 in mass ratio, additional amount 0.2%.Twin-screw Extruding machine draw ratio L/D=40,180-20 DEG C of screw rod heating temperature, 160-200 DEG C of static mixer temperature, melt pump intake pressure Power 100-150bar, technique water pressure 10bar or so, the temperature for having just enter into underwater cutpellet room is 50 DEG C or so, controls discharge pressure Difference (pressure difference of the process water i.e. in the high pressure hot melt of die head exit and underwater cutpellet room) 100-150bar.Multistage discharge is swollen In swollen technique water pipeline, the hydraulic pressure control 4 in first order technique water pipeline is 10bar or so, in the technique water pipeline of the second level Hydraulic pressure control is 7bar or so, and the hydraulic pressure in third level technique water pipeline is 4bar or so, the water in fourth stage technique water pipeline It is voltage-controlled to be made as 2bar or so.
Product is dripped after test, and waterproof and oilproof test reaches 5 grades, and watering test is 90 points of (Japanese Industrial Standards JIS)。
Embodiment 6
Compared with Example 1, the overwhelming majority is all identical, in addition to formula for raw stock is replaced are as follows:
Molecular weight MwIn the polyester-type thermoplastic polyurethane of 200K~300K (K herein indicates unit thousand, PLSCONFM), add Enter ratio 80% (weight percent, similarly hereinafter), molecular weight MwIn the polyester-type thermoplastic polyurethane of 50K~100K, additional proportion 15.9%, the additional amount of the organic perfluorinated material of environment-friendly degradable is 3%, and foaming agent is the CO that volume ratio 1:1 is added2With N2, it is added Amount 0.8%, nucleating agent are calcium carbonate and the tetrafluoroethene pulvis mixture of 1:1 in mass ratio, additional amount 0.3%.
Embodiment 7
Thermoplasticity of the invention is prepared according to following composition of raw materials and process conditions according to the above-mentioned process flow such as Fig. 1 Micro- balloon polymer elastomeric material:
The polyester-type thermoplastic polyurethane additional amount of shore hardness 80A is 80% (weight percent, similarly hereinafter), shore hardness It is 19.2% for the polyester-type thermoplastic polyurethane additional amount of 30A, the additional amount of the organic perfluorinated material of environment-friendly degradable is 0.2%, foaming agent selects CO2With N2By weight the mixing of 1:1, total additional amount is 0.4%, nucleating agent selection carbon nanotube, The mixing of talcum powder and calcium carbonate, total additional amount are 0.2%.
Bitruder draw ratio L/D=40,220 DEG C of screw rod heating temperature, 180 DEG C of static mixer temperature, melt Pump inlet pressure 100bar, technique water pressure 15bar or so, the technique coolant-temperature gage for having just enter into underwater cutpellet room is 60 DEG C or so, Control discharge pressure difference (pressure difference of the process water i.e. in the high pressure hot melt of die head exit and underwater cutpellet room) 95bar.It is multistage In discharge expansion process water pipeline, the hydraulic pressure control in first order technique water pipeline is 15bar or so, second level technique water pipeline In hydraulic pressure control be 7bar or so, the hydraulic pressure in third level technique water pipeline is 4bar or so, in fourth stage technique water pipeline Hydraulic pressure control be 2bar or so.
Embodiment 8
Compared with Example 7, the overwhelming majority is all identical, in addition to formula for raw stock is replaced are as follows:
The polyester-type thermoplastic polyurethane additional amount of shore hardness 85D is 60% (weight percent, similarly hereinafter), shore hardness It is 25% for the polyester-type thermoplastic polyurethane additional amount of 85A, the additional amount of the organic perfluorinated material of environment-friendly degradable is 5%, hair Infusion selects CO2With N2By weight the mixing of 1:1, total additional amount is 1%, and nucleating agent selects carbon nanotube, talcum powder and carbon The mixing of sour calcium, total additional amount are 9%.
Embodiment 9
Compared with Example 7, the overwhelming majority is all identical, in addition to high rigidity polyester-type thermoplastic polyurethane in formula for raw stock Shore hardness replace with 90A, the shore hardness of soft polyester-type thermoplastic polyurethane replaces with 50A.
Embodiment 10
Thermoplasticity of the invention is prepared according to following composition of raw materials and process conditions according to the above-mentioned process flow such as Fig. 1 Micro- balloon polymer elastomeric material:
Wherein, modified low-melting point polyester PET additional proportion 60% (weight percent, similarly hereinafter), polyester polyurethane are added Ratio 37%, the additional amount of the organic perfluorinated material of environment-friendly degradable are 2%, and nucleating agent is carbon black, additional amount 0.4%, foaming Agent is CO2With N2Mixing, additional amount 0.6%.
Bitruder draw ratio L/D=40,220-280 DEG C of screw rod heating temperature, static mixer temperature 180-250 DEG C, melt pump inlet pressure 100-150bar, technique water pressure 20bar or so have just enter into the technique coolant-temperature gage of underwater cutpellet room It is 90 DEG C or so, control discharge pressure difference (pressure difference of the process water i.e. in the high pressure hot melt of die head exit and underwater cutpellet room) 150-180bar.In multistage discharge expansion process water pipeline, the hydraulic pressure control in first order technique water pipeline is 20bar or so, Hydraulic pressure control in the technique water pipeline of the second level is 12bar or so, and the hydraulic pressure in third level technique water pipeline is 8bar or so, the Hydraulic pressure control in level Four technique water pipeline is 4bar or so.
Embodiment 11
Compared with Example 10, in addition to 260 DEG C of screw rod heating temperature, 240 DEG C of static mixer temperature outer, remaining is uniform Sample.
Embodiment 12
Compared with Example 10, other than it will be modified low-melting point polyester PET and replace with modified low melting point polyamide (PA), Yu Jun is the same.
Embodiment 13
Compared with embodiment 12, in addition to 300 DEG C of screw rod heating temperature, 260 DEG C of static mixer temperature outer, remaining is uniform Sample.
Embodiment 14
Compared with embodiment 12, in addition to 240 DEG C of screw rod heating temperature, 230 DEG C of static mixer temperature outer, remaining is uniform Sample.
Embodiment 15
Compared with Example 1, other than foaming agent is changed to normal butane, remaining is.
Embodiment 16
Compared with Example 1, other than foaming agent is changed to pentane, remaining is.
Embodiment 17
Compared with Example 1, other than foaming agent is changed to isopentane, remaining is.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention. Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention Within protection scope.

Claims (4)

1. a kind of degradable antifouling micro- balloon polymer elastomeric material of thermoplasticity, which is characterized in that including following weight percent Than the component of content: polymer raw material 88~98%, nucleating agent 0.05~0.5%, foaming agent 0.4~2%, environment-friendly degradable has Machine perfluorinated material 0.1~10%；
The polymer raw material by weight ratio content 60-95% support frame polymer material and weight ratio content 3-38% Pressure-resistant low resilience polymer material be composed, wherein support frame polymer material be molecular weight MwIt is 8 × 104~5 × 105High molecular weight polyurethane, it is corresponding pressure resistance low resilience polymer material be molecular weight MwIt is 2 × 104~2.5 × 105It is low Molecular weight polyisoprene urethane；
The polymer elastomer material is made by the following method:
(1) polymer raw material, nucleating agent and the organic perfluorinated material of environment-friendly degradable are fed from Bitruder front end feed opening Enter, foaming agent is fed from Bitruder middle section feed opening, after making each raw material hot melt mixing sufficiently, enters back into static mixer It further homogenizes, then again through Melt Pump pressure control and quantitative conveying；
(2) pelletizing of underwater cutpellet room is entered by die head by the hot melt that melt pumps out, and separation, gained is taken out of by process water Purpose product is formed after particle screen selecting is dry；
Technique coolant-temperature gage in step (2) in underwater cutpellet room is 10-90 DEG C, pressure 4-20bar；
When pelletizing is taken out of by process water, the multistage discharge expansion process water pipeline reduced step by step through excess pressure is conveyed；
Multistage discharge expansion process water pipeline is multi-stage process water pipeline in step (2), wherein the water of first order technique water pipeline Pressure keeps consistent with the technique water pressure of underwater cutpellet room is entered.
2. the degradable antifouling micro- balloon polymer elastomeric material of thermoplasticity of one kind according to claim 1, feature exist In the organic perfluorinated material of the environment-friendly degradable is selected from the PM-870 functionality master batch of 3M company.
3. the degradable antifouling micro- balloon polymer elastomeric material of thermoplasticity of one kind according to claim 1, feature exist In the nucleating agent is in carbon nanotube, silica, talcum powder, modified calcium carbonate, carbon black or tetrafluoroethene pulvis It is at least one；
The foaming agent is selected from CO2、N2, normal butane, at least one of pentane or isopentane.
4. the degradable antifouling micro- balloon polymer elastomeric material of thermoplasticity of one kind according to claim 1, feature exist In the temperature of Bitruder is 160~300 DEG C in step (1), and double screw extruder draw ratio is 32-56；
Temperature in static mixer is set as 120-260 DEG C, the inlet pressure 50-200bar of Melt Pump, and controls warp simultaneously The difference of the pressure of process water is 70-120bar in the hot melt pressure of die head extrusion and underwater cutpellet room.
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