CN107446343A - 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

Info

Publication number
CN107446343A
CN107446343A CN201710660143.9A CN201710660143A CN107446343A CN 107446343 A CN107446343 A CN 107446343A CN 201710660143 A CN201710660143 A CN 201710660143A CN 107446343 A CN107446343 A CN 107446343A
Authority
CN
China
Prior art keywords
pressure
polymer
thermoplasticity
polymeric material
micro
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710660143.9A
Other languages
Chinese (zh)
Other versions
CN107446343B (en
Inventor
陈乔健
郭杨龙
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nantong Deyi New Material Co Ltd
Original Assignee
Nantong Deyi New Material Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nantong Deyi New Material Co Ltd filed Critical Nantong Deyi New Material Co Ltd
Priority to CN201710660143.9A priority Critical patent/CN107446343B/en
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
Application granted granted Critical
Publication of CN107446343B publication Critical patent/CN107446343B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/08—Polyurethanes from polyethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B29B9/065—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion under-water, e.g. underwater pelletizers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B29B7/007—Methods for continuous mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/82—Heating or cooling
    • B29B7/826—Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/16—Auxiliary treatment of granules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0012—Combinations of extrusion moulding with other shaping operations combined with shaping by internal pressure generated in the material, e.g. foaming
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B29B2009/125—Micropellets, microgranules, microparticles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92514—Pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B29C2948/9259—Angular velocity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/06—CO2, N2 or noble gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/18—Binary blends of expanding agents
    • C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/05—Open cells, i.e. more than 50% of the pores are open
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2400/00—Characterised by the use of unspecified polymers
    • C08J2400/10—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08J2400/102—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C08J2475/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C08J2475/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/24—Crystallisation aids

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to a kind of degradable antifouling micro- balloon polymer elastomeric material of thermoplasticity, include the component of following weight percent content：Polymer raw material 88~98%, nucleator 0.05~0.5%, foaming agent 0.4~2%, the organic perfluorinated material 0.1~10% of environment-friendly degradable；Its preparation method is specially：(1) polymer raw material, nucleator and the organic perfluorinated material of environment-friendly degradable are fed from Bitruder front end charge door, foaming agent is fed from Bitruder stage casing charge door, after making each raw material hot melt mixing fully, enter 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, gained particle screen selecting forms purpose product after drying.Compared with prior art, the present invention can effectively realize the antifouling of material, bear dirty, oil resistant, anti-contamination is attractive in appearance, the performance such as good sense of touch, especially suitable for the application in the field such as footwear material and packaging for foodstuff.

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 area, polymerize more particularly, to a kind of degradable antifouling micro- air bag of thermoplasticity Thing elastomeric material and its preparation.
Background technology
Thermoplastic polymer elastomeric material manufactures facility, equipment, instrument and running stores used in production and life 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 popularization and application.But thermoplastic expanded polymer When elastomer directly applies to the direct consumer goods, without it is modified and special when, thermoplastic expanded conducting polymer rate is generally big 11 powers and the above in 10 cause to be also easy to produce electrostatic and Electrostatic Absorption, and it is difficult that solution outer surface is dry and astringent to make material, easily dirty The problems such as.Such as the foaming polyurethanes elastomer particle for sole, after consumer uses a period of time, sole surface can be stained with Contaminate a large amount of dusts, surface also can dirty as time went on and not easy cleaning.Because the material lightweight of the country has just started, institute With the antifouling modification to foamed thermoplastic polymer elastomer there is not yet research report and patent and report.
Thermoplastic polymer elastomeric material foaming and it is expanded after still need to possess good physical property, except requiring to expanded Material structure and material abscess etc., which are designed, afterwards outer also needs to antistatic, be designed on anti-pollution function.But it is limited by material Material structural property itself and processing technology, the understanding of foam theory and generating material are easily dirty, the understanding of easy dirty condition, cause state The interior material to expanded thermoplastic polymer elastomeric material does not temporarily control effectively and considered.
The content 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, include the group of following weight percent content Point：Polymer raw material 88-98%, nucleator 0.05~0.5%, foaming agent 0.4~2%, the organic perfluorinated material of environment-friendly degradable 0.1~10%.
As preferred embodiment, described support frame polymeric material be HMW, high rigidity, it is highly crystalline or Highly polar polymeric material, described pressure-resistant low resilience polymeric material are low point corresponding with support frame polymeric material Sub- amount, soft, low crystallize to amorphous state, low polarity to polar polymeric material.
As above-mentioned preferred embodiment it is further preferred that described support frame polymeric material is high-molecular-weight poly ammonia Ester, pressure-resistant low resilience polymeric material corresponding to it is low molecular weight polyurethane；
Or described support frame polymeric material is that high rigidity thermoplastic polymer elastomer (can be according to actual conditions Select such as TPU, TPE or rubber), pressure-resistant low resilience polymeric material corresponding to it is soft thermoplastic polymer elasticity Body；
Or described support frame polymeric material is polyamide or polyester, pressure-resistant low resilience polymeric material corresponding to it For thermoplastic polyurethane.
As above-mentioned further preferred embodiment still more preferably, the molecular weight M of described HMW polyurethanew For 8 × 104~5 × 105, the molecular weight M of low molecular weight polyurethanewFor 2 × 104~2.5 × 105；
The shore hardness of high rigidity thermoplastic polymer elastomer is 80A~75D soft thermoplastic polymer elastomers 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 to polymerize The fusing point difference of thing material and pressure-resistant resilience polymeric material is in 20 DEG C.It is furthermore preferred that modified low-melting point polyester can select such as Modified PET, PTT, PBT etc., modified low melting point polyamide can PA6, PA6I, PA11, PA12, PA9 that such as low melting point is modified.
As preferable technical scheme, the organic perfluorinated material of described environment-friendly degradable is the PM-870 work(selected from 3M companies Can sexupara grain.
As preferable technical scheme, described nucleator is selected from CNT, silica, talcum powder, modified carbonic acid At least one of calcium, carbon black or tetrafluoroethene pulvis；
Described 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 comprises the following steps：
(1) polymer raw material, nucleator and the organic perfluorinated material of environment-friendly degradable are fed from Bitruder front end Mouth feeding, foaming agent are fed from Bitruder stage casing charge door, after making 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, Gained particle screen selecting forms purpose product after drying.
As above-mentioned preferable technical scheme 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 hot melt pressure and underwater cutpellet room through die head extrusion.
As above-mentioned preferable technical scheme 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 release of pressure expansion process water pipeline reduced step by step through excess pressure conveys.
As the further preferred of above-mentioned further preferred embodiment, multistage release of pressure expansion process water pipeline in step (2) For multi-stage process water pipeline, wherein, the water pressure of first order technique water pipeline keeps the technique hydraulic pressure with entering underwater cutpellet room Power is consistent.Still more preferably, multistage release of pressure expansion process water pipeline is level Four technique water pipeline in step (2), wherein, the The hydraulic pressure of one-level 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 makes Bitruder be run in 50~900rpm rotating speeds under the driving of motor, the barrel setting of extruding machine 160~300 DEG C of temperature ensures that thermoplastic polymer can be heated fully, and polymer raw material, nucleator and environment-friendly degradable are organic complete Fluorine material is fed from front end screw rod charge door, and foaming agent is fed from the screw rod charge door in stage casing.After mixing extruding machine heat with And under the shearing force of screw rod, each material is melted by heat and fully enters static mixer afterwards in screw mixes, and melt is in static mixing The deep step of progress homogenizes in device and cooling ensures melt temperature between 120~260 DEG C, and can be required according to finished product physical property can Control.Acted on by the pressure control of Melt Pump and quantitative conveying, set Melt Pump inlet pressure control between 50~200bar it is crowded Melt pressure is stable in molding machine spiral shell thorax, makes fully mixed in controllable hyperbaric environment in the hot melt of mixed foaming agent and nucleator Close and be homogenized.It is by the push-in extruder die of hot high pressure Melt Stability, die head by Melt Pump pressure control and quantitative conveying function Porous AND DEWATERING FOR ORIFICE STRUCTURE, its inside ensure that heating physical efficiency stably passes through die head containing uniform heating facility.Sent out by Melt Pump high pressure Hot melt beans granular solid matter, underwater cutpellet are cut into by each hole grain-cutter that pelletizing room is rotated at a high speed under water of die head The grain-cutter of room really cuts hot melt under water.10~90 DEG C of process water produces 6 in the presence of technique water pump~ 20bar pressure 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 hydroecium Under be cooled rapidly and be cut into by grain-cutter granular.Due to pressure difference, and this between high pressure hot melt and high-pressure process water be present Kind pressure difference can be adjusted by the inlet pressure and frequency conversion technique water-aspirator pressure of Melt Pump so that be cut into grain in whole technique The polymer initial bubble speed and multiplying power of shape are controllable and stably.Because the cool 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 release of pressure expansion process water pipeline in the art, profit With the exocuticle of granular polymer, residence time longer intensity is higher in process water, the higher principle of pressure-bearing condition, first Still 4-20bar hydraulic pressure is maintained in level technique water pipeline, now granular melt portion cools down and under the conditions of existing for pressure difference Preliminary expansion.Greatly and shorten hydraulic pressure is down to 3~10bar by the change of pipeline diameter in the technique water pipeline of the second level, now The granular further cooled external intensity of melt rises but also can reflation after pressure difference change greatly.Lead in third level technique water pipeline Cross the change of pipeline diameter greatly and hydraulic pressure is down to 2~6bar by the drop low pipe resistance that shortens, now granular melt cools down again, and outer surface is strong Degree continue to rise but pressure difference become big after also reexpand but because grain crystalline is soon completed thus expansion rate be down to it is very low. Hydraulic pressure is down to 1~4bar to drop low pipe resistance in fourth stage technique water pipeline or by pipeline diameter and length adjustment, now Granular melt continues to cool down, and appearance surface intensity is further up but pressure difference still can yet be expanded after becoming big but because cool time Also crystallization completion makes the sizing of particle external diameter firm to very high and particle to enough particle exocuticle intensity substantially.It is granular it is expanded after Polymer enters in centrifugal separator jointly with water, herein water and expanded separate particles, and the particle after expansion, which enters, to shake Dynamic sieve enters after-treatment system, and process water exits into technique water tank from centrifugal separator.So repeatedly, make technique continuous Carry out.
Involved heavy polymer gathers with low-molecular weight polymer, high durometer polymeric and soft in the present invention Compound, high crystallinity polymer crystallize to amorphous state polymer, highly polar polymer and rudimentary property or polar polymeric with low Deng HMW and low molecule amount in combination etc. made a distinction by the different two kinds of polymer material contrast of physical property, i.e., The two kinds of polymer raw material of different physical property, molecular weight it is higher be defined as heavy polymer, relatively low then fixed of molecular weight Justice is low-molecular weight polymer, and similarly, high rigidity and soft etc. are also analogy definition.It is furthermore preferred that HMW polymerize The molecular weight of thing is at least twice the above than low-molecular weight polymer；The hardness of high durometer polymeric should be than soft polymer Poor more than 10A.
Preferably, playing the pressure-resistant resilience polymeric material of rebound effect should select elastomer to birds of the same feather flock together compound material, as TPU, Rubber, TPE etc., the support frame polymeric material to play a supportive role can be that elastomer be birdsed of the same feather flock together compound material, can also select 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 people in the art Raw material or technology known to member.As thermoplastic polyurethane can be used by directly using commercially available prod or according to known work It is prepared by skill technology oneself.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, by designing and controlling the micro- gas in the inside of 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 go out the pressure of extruding machine to control bubble swelling of nucleus, finally, Foam solidifying and setting is controlled by the method for melt pressure and process water pressure differential and process water sustained release pressure.
Preferably, the present invention is gathered on raw material by designing heavy polymer with low-molecular weight polymer, high rigidity Compound crystallizes to amorphous state polymer, highly polar polymer and rudimentary property with soft polymer, high crystallinity polymer with low Or polar polymeric is respectively combined, foaming agent then is added after blending hot melt, then after controllable bulking process, utilizes hair The difference of foaming capacity of the infusion in different physical property polymer raw materials, obtain atomic closed airbag structure support component and opening Foam component collectively constitutes the netted composite puffed material of IPN air passage structure of winding.Wherein, by HMW or high rigidity or Formed in the presence of nucleator countless 0.01~20 micron of highly crystalline or highly polar polymeric material and foaming agent it is small Closed air bag, and serve as support component in bulking meterial by these small closed air bags, and low molecule or soft or low knot Brilliant or low polarity/polar polymeric then forms superfine micro- open cells (non-closed pore) with foaming agent, and with expanded group of part 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 Partly connected between road and extend to bulking meterial particle surface.So, 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 assigns bulking meterial good extruding soft feeling, and more preferable stability of strutting system；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.Whole material can integrally obtain Preferably buffering feedback.
In addition, the present invention can also utilize different foaming agents oozing in different polymeric materials in 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 The difference that physical property change is retained with transitivity after change, so as to control it is expanded after material in micro- air bag size and how many, Yi Jikai How much mouthful cell size, shape and reach adjusting the physical property of material and meet the purposes of different downstream uses and customer requirement.
The present invention is in 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, so as to increase die entrance pressure indirectly, and accelerate to release by technique water pressure Pressure.When needing to reduce perforate or open cells ratio, under Constant process coolant-temperature gage, reduce melt booster pump inlet pressure, Reduce die entrance pressure indirectly, and pass through process water pressure relieving release of pressure.
Compared with prior art, the present invention has advantages below：
(1) present invention is to the composition of raw materials of thermoplastic polymer elastomeric material by being designed, and makes to possess height in itself and leads The material surface polarity of electric rate diminishes, and then the body for improving material is grease proofing, antifouling, water resistance, simultaneously so that sense of touch rises. In the present invention, select to disperse to add when polymeric material synthesizes by modified environment-friendly degradable type perfluorinated material, make the environmental protection Degradable perfluorinated material can be well dispersed in material system, and realizes that reduction is led by being separated in subsequent technique Electric rate and polarity are uniformly distributed.Enable environment-friendly degradable type perfluorinated material to form ion by subsequent treatment and bulking process to become It is grease proofing so as to improve the antifouling of expanded thermoplastic surface of polymer material to reducing conductance and surface polarity, waterproof and touch Sense.
(2) thermoplastic, polymeric materials produced by the present invention can be widely used in the fields such as footwear material and packaging for foodstuff.
(3) bulking meterial of closed micropore made of single physical property polymer raw materials, the present invention are used compared in general Using two kinds of different physical property polymer composition polymer raw materials, it is set to be formed during puffing foaming with suitable micro- air bag The open cells of structure and appropriateness form winding network air flue interpenetrating structure, and so, micro- airbag structure can provide very for material Good physical property, such as intensity, modulus of elasticity and screen resilience, and open cells structure can then improve the energy-absorbing energy storage of material Property, contact sense and comfort.
(4) by the adjustment to formula and adjustment of technology can effectively adjust micro- air bag and open cells structure, Opening form and density, size etc., and can effectively control micro- air bag in material to account for 20~99.5% of volume or so, opening Abscess accounts for 0.5~80% of material volume or so.
(5) can be by controlling the back pressure of the hot melt in Bitruder and cutting under water in preparation process of the invention The back pressure of grain room stablizes release of pressure expanded speed and multiplying power, reaches the requirement for being precisely controlled material expand multiplying power.
(6) using the process of multistage progressively release of pressure, can flexibly control brokenly bubble rate in different polymer expansion processes will Ask so as to reach the suitable composite puffed structural material of manufacture.
(7) polymer elastomer material prepared by the present invention is applied to article of footwear, packaging, damping, insulation, seat, race The expanded material application field such as road, solid tyre.
Brief description of the drawings
Fig. 1 is the process chart of the present 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- motors, 2- Bitruders, 3- spouts one, 4- spouts two, 5- static mixers, 6- melts Pump, 7- die heads, 8- underwater cutpellets room, 9- process water inlet tubes, 10- process water one-level release of pressure pipes, 11- process water two level releases of pressure Pipe, 12- process water three-level release of pressure pipes, 13- process water level Four release of pressure pipes, 14- centrifugal separators, 15- vibratory sieves, 16- techniques Water pump component.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
It is necessarily pointed out that implementation below is served only for embodiment, the invention will be further described, no It is understood that and is made for limiting the scope of the invention, professional and technical personnel in the field according to the content of the invention described above Some nonessential modifications and adaptations, still fall within protection scope of the present invention.
In addition, if without other explanations, raw materials used is all commercially available.
Participate in the election of the detailed description of the invention below for being preferable to carry out method and including embodiment this hair can be more easily understood Bright content.Unless otherwise defined, all technologies used herein and scientific terminology have common with art of the present invention The identical implication that technical staff is generally understood that.When contradiction be present, the definition in this specification is defined.
As used herein term " by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " comprising ", " having ", " containing " or its any other deformation, it is intended that cover including for non-exclusionism.For example, the combination comprising listed elements Thing, step, method, product or device are not necessarily limited to those key elements, but can include not expressly listed other key elements or Such a composition, step, method, product or the intrinsic key element of device.
Equivalent, concentration or other values or parameter are excellent with scope, preferred scope or a series of upper limit preferred values and lower limit During the Range Representation that choosing value limits, this, which is appreciated that, specifically discloses by any range limit or preferred value and any scope All scopes that any pairing of lower limit or preferred value is formed, regardless of whether the scope separately discloses.For example, when open During scope " 1 to 5 ", described scope should be interpreted as including scope " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to 5 ", " 1 to 3 and 5 " etc..When number range is described herein, unless otherwise indicated, otherwise the scope is intended to include its end Value and all integers and fraction within the range.
Approximate term in specification and claims is used for modifying quantity, and it is specific to represent that the present invention is not limited to this Quantity, include the part of the amendment of the acceptable change without cause related basic function close to the quantity.Phase Answer, modify a numerical value with " about ", " about " etc., mean that the invention is not restricted to the exact numerical.It is approximate in some examples Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, scope limits can be with Combine and/or exchange, these scopes include all subranges contained therebetween if not stated otherwise.
In addition, indefinite article " one kind " before key element of the present invention or component and "one" to key element or the quantitative requirement of component (i.e. occurrence number) unrestriction.Therefore "one" or " one kind " should be read as including one or at least one, and odd number The key element or component of form also include plural form, unless the obvious purport of the quantity refers to singulative.
" polymer " means by the polymerizable compound prepared by the monomer that polymerize identical or different type.Generic term " polymer " includes term " homopolymer ", " copolymer ", " terpolymer " and " EVA ".
A kind of degradable antifouling micro- balloon polymer elastomeric material of thermoplasticity, include the group of following weight percent content Point：Polymer raw material 88-98%, nucleator 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, described polymer raw material is by support frame polymeric material (60-95%) Combined with pressure-resistant low resilience polymeric material (3-38%), wherein, described support frame polymeric material is macromolecule Amount, high rigidity, highly crystalline or highly polar polymeric material, described pressure-resistant low resilience polymeric material is polymerize with support frame The corresponding low molecule amount of thing material, soft, low crystallize to amorphous state, low polarity/polar polymeric material.
As above-mentioned preferred embodiment it is further preferred that described support frame polymeric material is high-molecular-weight poly ammonia Ester, pressure-resistant low resilience polymeric material corresponding to it is low molecular weight polyurethane；
Or described support frame polymeric material is that high rigidity thermoplastic polymer elastomer (can be according to actual conditions Select such as TPU, TPE or rubber), pressure-resistant low resilience polymeric material corresponding to it is soft thermoplastic polymer elasticity Body；
Or described support frame polymeric material is polyamide or polyester, pressure-resistant low resilience polymeric material corresponding to it For thermoplastic polyurethane.
As above-mentioned further preferred embodiment still more preferably, the molecular weight M of described HMW polyurethanew For 8 × 104~5 × 105, the molecular weight M of low molecular weight polyurethanewFor 2 × 104~2.5 × 105；
The shore hardness of high rigidity thermoplastic polymer elastomer is 80A~75D soft thermoplastic polymer elastomers 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 to polymerize The fusing point difference of thing material and pressure-resistant resilience polymeric material is in 20 DEG C.It is furthermore preferred that modified low-melting point polyester can select such as Modified PET, PTT, PBT etc., modified low melting point polyamide can PA6, PA6I, PA11, PA12, PA9 that such as low melting point is modified.
As preferable technical scheme, the organic perfluorinated material of described environment-friendly degradable is selected from the PM-870 functions of 3M companies Sexupara grain.
As preferable technical scheme, described nucleator is selected from CNT, silica, talcum powder, modified carbonic acid At least one of calcium, carbon black or tetrafluoroethene pulvis；
Described 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 comprises the following steps：
(1) polymer raw material, nucleator and the organic perfluorinated material of environment-friendly degradable are fed from Bitruder front end Mouth feeding, foaming agent are fed from Bitruder stage casing charge door, after making 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, Gained particle screen selecting forms purpose product after drying.
As above-mentioned preferable technical scheme 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 extruded through die head The difference of the pressure of process water is 70-120bar in melt pressure and underwater cutpellet room.
As above-mentioned preferable technical scheme 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 release of pressure expansion process water pipeline reduced step by step through excess pressure conveys.
Further preferred, multistage release of pressure expansion process water pipeline in step (2) as above-mentioned preferred technical scheme 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 accompanying drawing 1 of the detailed description of above-mentioned preparation process, Bitruder 2 is under the driving of motor 1 Run with 50~900rpm rotating speeds, 160~300 DEG C of the barrel design temperature of Bitruder 2 ensures thermoplastic polymer energy Fully hot melt, polymer raw material and nucleator are fed from the spout 1 of front end, and foaming agent is fed from the spout 24 in stage casing. After mixing under the shearing force of heating and screw rod, each raw material is melted by heat and fully enters static mixer 5 afterwards in screw mixes, Melt carries out that a deep step homogenizes and cooling ensures that melt temperature between 120~280 DEG C, specifically may be used in static mixer 5 Require controllable according to finished product physical property.Acted on by the pressure control and quantitative conveying of Melt Pump 6 (gear pump etc. can be used), set melt The inlet pressure of pump 6 controls melt pressure stabilization in the spiral shell thorax of Bitruder 2, makes mixed foaming between 50~200bar It is sufficiently mixed and is homogenized in controllable hyperbaric environment in the hot melt of agent and nucleator.By the pressure control of Melt Pump 6 and quantify defeated Sending function, die head 7 be porous AND DEWATERING FOR ORIFICE STRUCTURE, and it is internal containing uniformly by the die head 7 of the push-in extruding machine of hot high pressure Melt Stability Heating facility ensures to heat physical efficiency stably by die head 7.Each hole that die head 7 is passed through by the hot melt that the high pressure of Melt Pump 6 is sent out The grain-cutter that pelletizing room 8 is rotated at a high speed under water is cut into beans granular solid matter, and the grain-cutter of underwater cutpellet room 8 is really under water Cut hot melt.10~90 DEG C of process water produces 4 in the presence of technique water pump component 16 (comprising water pump and water tank etc.)~ 15bar pressure, and underwater cutpellet room 8 is entered by process water water inlet pipe 9.The high pressure hot melt extruded so at die head 7 It is cooled rapidly and is cut into 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 being cut into granular polymer initial bubble speed in whole technique and multiplying power is controllable and stably.Because that has just cut is granular Cool time of polymer is short and different formulations in material crystalline speed it is widely different, be specifically designed multistage in the art Release of pressure 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, is still tieed up in first order technique water pipeline (i.e. process water one-level release of pressure pipe 10) 4~15bar hydraulic pressure is held, now granular melt portion is cooled down and tentatively expanded under the conditions of existing for pressure difference.In second level work Greatly and shorten hydraulic pressure is down to 3~10bar by the change of pipeline diameter in skill water pipeline (i.e. process water two level release of pressure pipe 11), this When the further cooled external intensity of granular melt rise but pressure difference become big after also can reflation.In third level technique water pipeline Hydraulic pressure is down to by 2~6bar with the drop low pipe resistance that shortens by the change of pipeline diameter greatly in (i.e. process water three-level release of pressure pipe 12), this When granular melt cool down again, appearance surface intensity continue to rise but pressure difference become big after also reexpand 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 release of pressure pipe 13) Hydraulic pressure is down to 1~4bar by linear diameter and length adjustment to drop low pipe resistance, and now granular melt continues to cool down, and appearance surface intensity is entered One step rises but pressure difference still can yet expand after becoming big but because cool time enough particle exocuticle intensity it is very high and Also crystallization completion makes the sizing of particle external diameter firm to particle substantially.It is granular it is expanded after polymer and water separated jointly into centrifugal In machine 14, water and expanded rear particle product separation, the particle after expansion enter vibratory sieve 15 and enter after-treatment system simultaneously herein Expanded finished product output is generated, process water exits into technique water pump component 16 from centrifugal separator 14.So repeatedly, work is made Skill is carried out continuously.
In addition it should be pointed out that, disclosed above is only the basic components of the present 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 being actually needed, and such as add anti- Oxidant and age resister etc. improve the ageing resistace of product.
In following each embodiments, used polyether thermoplastic polyurethane is from Baeyer, Hensel Mai Deng producers；Adopted Polyester-type thermoplastic polyurethane is from Baeyer, Hensel Mai Deng producers；Used modified low-melting point polyester PET is derived from Kingsoft petrochemical industry etc.；Used modified low melting point polyamide is from Du Pont, Ying Chuandeng companies；Used PBT is from gold The companies such as mountain petrochemical industry.
Embodiment 1
According to the above-mentioned thermoplasticity for preparing the present invention according to following composition of raw materials and process conditions such as Fig. 1 technological process Micro- balloon polymer elastomeric material：
Wherein, molecular weight MwIn the polyether thermoplastic polyurethane of 150K~300K (K herein represents unit thousand), add Ratio 75% (percetage by weight, similarly hereinafter), molecular weight MwIn 50K~100K polyether thermoplastic polyurethane, additional proportion 20%, The addition of the organic perfluorinated material of environment-friendly degradable is 2.5%, foaming agent CO2, addition 2%, nucleator is calcium carbonate, is added Enter amount for 0.5%.Bitruder draw ratio L/D=40,160-220 DEG C of screw rod heating-up temperature, static mixer temperature 140-180 DEG C, melt pump inlet pressure 100-150bar, technique water pressure 12bar or so, the work having just enter into underwater cutpellet room Skill coolant-temperature gage is 30 DEG C, control release of pressure pressure difference (the i.e. pressure of the high pressure hot melt of die head exit and the process water in underwater cutpellet room Power is poor) 100-150bar.In multistage release of pressure expansion process water pipeline, the hydraulic pressure control in first order technique water pipeline is 12bar Left and right, the hydraulic pressure control in the technique water pipeline of the second level are 8bar or so, and the hydraulic pressure in third level technique water pipeline is left for 5bar The right side, the hydraulic pressure control in fourth stage technique water pipeline are 2bar or so.
The SEM pictures of product particle 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, after test of dripping, waterproof and oilproof test reaches 5 grades, and watering test is 90 points of (Japanese Industrial Standards JIS)。
Embodiment 2
According to the above-mentioned thermoplasticity for preparing the present invention according to following composition of raw materials and process conditions such as Fig. 1 technological process Micro- balloon polymer elastomeric material：
Wherein, molecular weight MwIn 300K~500K polyether thermoplastic the polyurethane, (weight percent of additional proportion 70% Number, similarly hereinafter), molecular weight MwIn 150K~250K polyether thermoplastic polyurethane, additional proportion 18.1%, environment-friendly degradable is organic The addition of perfluorinated material is 10%, foaming agent N2, addition 1.4%, nucleator is carbon black, addition 0.5%.Double spiral shells Bar extruding machine draw ratio L/D=56,160-220 DEG C of screw rod heating-up temperature, 140-180 DEG C of static mixer temperature, melt is pumped into Mouth pressure 100-150bar, technique water pressure 6bar or so, the process water temperature control for having just enter into underwater cutpellet room are 60 DEG C, control Release of pressure pressure difference (i.e. the pressure differential of the high pressure hot melt of die head exit and the process water in underwater cutpellet room) 90-150bar processed.It is more In level release of pressure expansion process water pipeline, 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 for 1bar or so.
Product is after test of dripping, and waterproof and oilproof test reaches 5 grades, and watering test is 90 points of (Japanese Industrial Standards JIS)。
Embodiment 3
According to the above-mentioned thermoplasticity for preparing the present invention according to following composition of raw materials and process conditions such as Fig. 1 technological process Micro- balloon polymer elastomeric material：
Wherein, molecular weight MwIn 80K~120K polyether thermoplastic polyurethane, additional proportion 90% (percetage by weight, Similarly hereinafter), molecular weight MwIn 20K~50K polyether thermoplastic polyurethane, additional proportion 9%, the organic perfluorinated material of environment-friendly degradable Addition be 0.1%, foaming agent N2, addition 0.4%, nucleator is talcum powder and modified calcium carbonate in mass ratio 1:1 Mixture, addition 0.5%.Bitruder draw ratio L/D=38,160-220 DEG C of screw rod heating-up 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 release of pressure pressure difference is (i.e. in the high pressure hot melt of die head exit and underwater cutpellet room The pressure differential of process water) 90-140bar.In multistage release of pressure expansion process water pipeline, the Water pressure controlled 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 Press as 6bar or so, the hydraulic pressure control in fourth stage technique water pipeline is 4bar or so.
Product is after test of dripping, and waterproof and oilproof test reaches 5 grades, and watering test is 90 points of (Japanese Industrial Standards JIS)。
Embodiment 4
According to the above-mentioned thermoplasticity for preparing the present invention according to following composition of raw materials and process conditions such as Fig. 1 technological process Micro- balloon polymer elastomeric material：
Wherein, molecular weight MwIn 80K~120K polyether thermoplastic polyurethane, additional proportion 65% (percetage by weight, Similarly hereinafter), molecular weight MwIn 20K~50K polyether thermoplastic polyurethane, additional proportion 25%, the organic perfluor material of environment-friendly degradable The addition of material is 8%, foaming agent N2, addition 1.8%, nucleator is CNT, addition 0.2%.Twin-screw Extruding machine draw ratio L/D=52,160-220 DEG C of screw rod heating-up 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 are 30 DEG C or so, control Release of pressure pressure difference (i.e. the pressure differential of the high pressure hot melt of die head exit and the process water in underwater cutpellet room) 90-150bar processed.It is more In level release of pressure expansion process water pipeline, 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 for 2bar or so.
Product is after test of dripping, and waterproof and oilproof test reaches 5 grades, and watering test is 90 points of (Japanese Industrial Standards JIS)。
Embodiment 5
According to the above-mentioned thermoplasticity for preparing the present invention according to following composition of raw materials and process conditions such as Fig. 1 technological process Micro- balloon polymer elastomeric material：
Wherein, molecular weight MwIn the poly- ammonia of polyether thermoplastic of 120K~180K (K herein represents unit thousand, PLSCONFM) Ester, additional proportion 95% (percetage by weight, similarly hereinafter), molecular weight MwIn 20K~50K polyether thermoplastic polyurethane, ratio is added Example 3%, the addition of the organic perfluorinated material of environment-friendly degradable is 1%, and foaming agent is volume ratio 1:1 CO added2With N2, add Amount 0.8%, nucleator are calcium carbonate and tetrafluoroethene pulvis in mass ratio 1:1 mixture, addition 0.2%.Twin-screw Extruding machine draw ratio L/D=40,180-20 DEG C of screw rod heating-up 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 are 50 DEG C or so, control release of pressure pressure Difference (i.e. the pressure differential of the high pressure hot melt of die head exit and the process water in underwater cutpellet room) 100-150bar.Multistage release of pressure 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 after test of dripping, 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, except formula for raw stock replaces with：
Molecular weight MwIn the polyester-type thermoplastic polyurethane of 200K~300K (K herein represents unit thousand, PLSCONFM), add Enter ratio 80% (percetage by weight, similarly hereinafter), molecular weight MwIn 50K~100K polyester-type thermoplastic polyurethane, additional proportion 15.9%, the addition of the organic perfluorinated material of environment-friendly degradable is 3%, and foaming agent is volume ratio 1:1 CO added2With N2, add Amount 0.8%, nucleator are calcium carbonate and tetrafluoroethene pulvis in mass ratio 1:1 mixture, addition 0.3%.
Embodiment 7
According to the above-mentioned thermoplasticity for preparing the present invention according to following composition of raw materials and process conditions such as Fig. 1 technological process Micro- balloon polymer elastomeric material：
Shore hardness 80A polyester-type thermoplastic polyurethane addition is 80% (percetage by weight, similarly hereinafter), shore hardness It is 19.2% for 30A polyester-type thermoplastic polyurethane addition, the addition of the organic perfluorinated material of environment-friendly degradable is 0.2%, foaming agent selects CO2With N2By weight 1:1 mixing, its total addition be 0.4%, nucleator from CNT, The mixing of talcum powder and calcium carbonate, total addition are 0.2%.
Bitruder draw ratio L/D=40,220 DEG C of screw rod heating-up 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 are 60 DEG C or so, Control release of pressure pressure difference (i.e. the pressure differential of the high pressure hot melt of die head exit and the process water in underwater cutpellet room) 95bar.It is multistage In release of pressure expansion process water pipeline, hydraulic pressure control in first order technique water pipeline is 15bar or so, second level technique water pipeline In hydraulic pressure control for 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 for 2bar or so.
Embodiment 8
Compared with Example 7, the overwhelming majority is all identical, except formula for raw stock replaces with：
Shore hardness 85D polyester-type thermoplastic polyurethane addition is 60% (percetage by weight, similarly hereinafter), shore hardness It is 25% for 85A polyester-type thermoplastic polyurethane addition, the addition of the organic perfluorinated material of environment-friendly degradable is 5%, hair Infusion selects CO2With N2By weight 1:1 mixing, its total addition are 1%, and nucleator selects CNT, talcum powder and carbon The mixing of sour calcium, total addition are 9%.
Embodiment 9
Compared with Example 7, the overwhelming majority is all identical, except 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
According to the above-mentioned thermoplasticity for preparing the present invention according to following composition of raw materials and process conditions such as Fig. 1 technological process Micro- balloon polymer elastomeric material：
Wherein, modified low-melting point polyester PET additional proportions 60% (percetage by weight, similarly hereinafter), PAUR add Ratio 37%, the addition of the organic perfluorinated material of environment-friendly degradable is 2%, and nucleator is carbon black, addition 0.4%, is foamed Agent is CO2With N2Mixing, its addition be 0.6%.
Bitruder draw ratio L/D=40,220-280 DEG C of screw rod heating-up 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 For 90 DEG C or so, control release of pressure pressure difference (i.e. the pressure differential of the high pressure hot melt of die head exit and the process water in underwater cutpellet room) 150-180bar.In multistage release of pressure 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, except 260 DEG C of screw rod heating-up temperature, 240 DEG C of static mixer temperature is outer, and remaining is homogeneous Sample.
Embodiment 12
Compared with Example 10, in addition to modified low-melting point polyester PET is replaced with into modified low melting point polyamide (PA), its Yu Jun is the same.
Embodiment 13
Compared with embodiment 12, except 300 DEG C of screw rod heating-up temperature, 260 DEG C of static mixer temperature is outer, and remaining is homogeneous Sample.
Embodiment 14
Compared with embodiment 12, except 240 DEG C of screw rod heating-up temperature, 230 DEG C of static mixer temperature is outer, and remaining is homogeneous Sample.
Embodiment 15
Compared with Example 1, in addition to foaming agent is changed into normal butane, remaining is.
Embodiment 16
Compared with Example 1, in addition to foaming agent is changed into pentane, remaining is.
Embodiment 17
Compared with Example 1, in addition to foaming agent is changed into isopentane, remaining is.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using invention. Person skilled in the art obviously can easily make various modifications to these embodiments, and described herein general Principle is applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to above-described embodiment, ability Field technique personnel do not depart from improvement that scope made and modification all should be the present invention's according to the announcement of the present invention Within protection domain.

Claims (10)

1. a kind of degradable antifouling micro- balloon polymer elastomeric material of thermoplasticity, it is characterised in that including following weight percent Than the component of content：Polymer raw material 88~98%, nucleator 0.05~0.5%, foaming agent 0.4~2%, environment-friendly degradable has Machine perfluorinated material 0.1~10%.
2. the degradable antifouling micro- balloon polymer elastomeric material of thermoplasticity of one kind according to claim 1, its feature exist In, described polymer raw material is combined by support frame polymeric material and pressure-resistant low resilience polymeric material, wherein, branch Support bone frame polymeric material is HMW, high rigidity, highly crystalline or highly polar polymeric material, pressure-resistant low resilience polymeric material Expect for the low molecule amount corresponding with support frame polymeric material, soft, low crystallize to amorphous state, low polarity to electrodeless Property polymeric material.
3. the degradable antifouling micro- balloon polymer elastomeric material of thermoplasticity of one kind according to claim 2, its feature exist In described support frame polymeric material is high molecular weight thermoplastic polyurethanes, pressure-resistant resilience polymeric material corresponding to it For low molecular weight thermoplastic polyurethane；
Or described support frame polymeric material is high rigidity thermoplastic polymer elastomer, pressure-resistant low resilience corresponding to it gathers Compound material is soft thermoplastic polymer elastomer；
Or described support frame polymeric material is polyamide or polyester, pressure-resistant low resilience polymeric material corresponding to it is heat Plastic polyurethane.
4. the degradable antifouling micro- balloon polymer elastomeric material of thermoplasticity of one kind according to claim 3, its feature exist In the molecular weight M of described HMW polyurethanewFor 8 × 104~5 × 105, the molecular weight M of low molecular weight polyurethanewFor 2 ×104~2.5 × 105；
The shore hardness of high rigidity thermoplastic polymer elastomer is 80A~75D, Shao of soft thermoplastic polymer elastomer Family name's hardness is 30~85A；
Polyester or polyamide are respectively modified low-melting point polyester or modified low melting point polyamide, and control support frame polymeric material The fusing point difference of material and pressure-resistant resilience polymeric material is in 20 DEG C.
5. the degradable antifouling micro- balloon polymer elastomeric material of thermoplasticity of one kind according to claim 1, its feature exist In the organic perfluorinated material of described environment-friendly degradable is selected from the PM-870 feature master batches of 3M companies.
6. the degradable antifouling micro- balloon polymer elastomeric material of thermoplasticity of one kind according to claim 1, its feature exist In described nucleator is in CNT, silica, talcum powder, modified calcium carbonate, carbon black or tetrafluoroethene pulvis It is at least one；
Described foaming agent is selected from CO2、N2, normal butane, at least one of pentane or isopentane.
7. the preparation side of the degradable antifouling micro- balloon polymer elastomeric material of thermoplasticity as described in claim 1-6 is any Method, it is characterised in that comprise the following steps：
(1) polymer raw material, nucleator and the organic perfluorinated material of environment-friendly degradable are fed from Bitruder front end charge door Enter, foaming agent is fed from Bitruder stage casing charge door, after making each raw material hot melt mixing fully, enters back into static mixer Further 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, gained is taken out of by process water Particle screen selecting forms purpose product after drying.
8. a kind of preparation method of the micro- balloon polymer elastomeric material of thermoplasticity according to claim 7, its 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.
9. a kind of preparation method of the micro- balloon polymer elastomeric material of thermoplasticity according to claim 7, its feature exist In 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 release of pressure expansion process water pipeline reduced step by step through excess pressure conveys.
10. a kind of preparation method of the micro- balloon polymer elastomeric material of thermoplasticity according to claim 9, its feature exist In, multistage release of pressure 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 for entering underwater cutpellet room.
CN201710660143.9A 2017-08-04 2017-08-04 A kind of micro- balloon polymer elastomeric material of degradable antifouling thermoplasticity and its preparation Active CN107446343B (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201710660143.9A CN107446343B (en) 2017-08-04 2017-08-04 A kind of micro- balloon polymer elastomeric material of degradable antifouling thermoplasticity and its preparation
CN201811081676.2A CN109320951B (en) 2017-08-04 2017-08-04 Degradable antifouling thermoplastic micro-balloon polymer elastomer material and preparation method thereof
PCT/CN2018/088920 WO2019024588A1 (en) 2017-08-04 2018-05-30 Degradable antifouling thermoplastic micro-airbag polymer elastomer material and preparation thereof
PCT/CN2018/098027 WO2019024869A1 (en) 2017-08-04 2018-08-01 Degradable antifouling thermoplastic micro-airbag polymer elastomer material and preparation therefor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710660143.9A CN107446343B (en) 2017-08-04 2017-08-04 A kind of micro- balloon polymer elastomeric material of degradable antifouling thermoplasticity and its preparation

Related Child Applications (1)

Application Number Title Priority Date Filing Date
CN201811081676.2A Division CN109320951B (en) 2017-08-04 2017-08-04 Degradable antifouling thermoplastic micro-balloon polymer elastomer material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN107446343A true CN107446343A (en) 2017-12-08
CN107446343B CN107446343B (en) 2019-03-08

Family

ID=60489973

Family Applications (2)

Application Number Title Priority Date Filing Date
CN201811081676.2A Active CN109320951B (en) 2017-08-04 2017-08-04 Degradable antifouling thermoplastic micro-balloon polymer elastomer material and preparation method thereof
CN201710660143.9A Active CN107446343B (en) 2017-08-04 2017-08-04 A kind of micro- balloon polymer elastomeric material of degradable antifouling thermoplasticity and its preparation

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN201811081676.2A Active CN109320951B (en) 2017-08-04 2017-08-04 Degradable antifouling thermoplastic micro-balloon polymer elastomer material and preparation method thereof

Country Status (2)

Country Link
CN (2) CN109320951B (en)
WO (2) WO2019024588A1 (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107722602A (en) * 2017-09-26 2018-02-23 上海德亿化工有限公司 Foamed profile of Memorability multiple spot positive feedback resilient material and preparation method thereof
CN107746570A (en) * 2017-09-26 2018-03-02 上海德亿化工有限公司 A kind of polyamide expanded material its preparation method
CN108864662A (en) * 2018-07-25 2018-11-23 南通德亿新材料有限公司 A kind of thermoplastic polyether ester elastomer foamed material and preparation method thereof
CN109228003A (en) * 2018-09-19 2019-01-18 福建鑫瑞新材料科技有限公司 A kind of device and method preparing low-density polymeric foam beads using overcritical fluid-mixing extrusion foaming
WO2019024869A1 (en) * 2017-08-04 2019-02-07 南通德亿新材料有限公司 Degradable antifouling thermoplastic micro-airbag polymer elastomer material and preparation therefor
WO2019024868A1 (en) * 2017-08-04 2019-02-07 南通德亿新材料有限公司 Thermoplastic micro-sac polymer elastomer material and preparation method therefor
WO2019024870A1 (en) * 2017-08-04 2019-02-07 南通德亿新材料有限公司 Micro-particle-size thermoplastic micro-airbag polyurethane elastomer material and preparation therefor

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101245159A (en) * 2008-03-28 2008-08-20 天津市润达塑料包装有限公司 Process for manufacturing polyolefin foaming particle material
CN102056967A (en) * 2008-06-12 2011-05-11 3A科技和管理有限公司 Foamed polyesters and methods for their production
CN103709726A (en) * 2013-12-17 2014-04-09 烟台开发区新龙华包装材料有限公司 Extrusion foaming thermoplastic polyurethane elastomer bead and preparation method thereof
CN103804890A (en) * 2014-02-18 2014-05-21 山东美瑞新材料有限公司 Extruded foaming thermoplastic polyurethane elastomer particles and preparation method thereof
CN104877335A (en) * 2015-05-06 2015-09-02 丁钰 Thermoplastic polyurethane elastomer foamed bead and preparation method thereof
CN104974370A (en) * 2015-01-19 2015-10-14 常州市顺祥新材料科技有限公司 Preparation method of thermoplastic polyurethane beads and bead molding technology
CN105592997A (en) * 2013-08-16 2016-05-18 比瑞塑料公司 Polymeric material for an insulated container
CN106541508A (en) * 2016-08-19 2017-03-29 浙江佳阳塑胶新材料有限公司 A kind of method that endothermic blowing agent prepares expanded bead with reference to supercritical nitrogen

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19823626B4 (en) * 1998-05-27 2007-01-11 Dupont Dow Elastomers L.L.C., Wilmington Partly crosslinked, thermoplastic polymer material
DE19860205A1 (en) * 1998-12-24 2000-06-29 Basf Ag Composite elements containing (i) thermoplastic polyurethanes and (ii) microcellular polyurethane elastomers
BRPI0722016A2 (en) * 2007-09-19 2014-03-25 Henkel Ag & Co. Kgaa HIGHLY EXPANDABLE MATERIAL AND DEVICES AND SHOCKERS
CN102276785B (en) * 2011-07-12 2013-01-30 山东奥邦聚氨酯有限公司 Low-density foamed thermoplastic polyurethane elastic body and preparation process thereof
PL3578597T3 (en) * 2012-04-13 2021-09-13 Basf Se Method for the production of expanded granules
BR112015031074B8 (en) * 2013-06-13 2021-02-23 Basf Se process to produce expanded pellets
CN103804889B (en) * 2014-02-18 2016-01-27 山东美瑞新材料有限公司 A kind of foamed thermoplastic polyurethane particle and its preparation method and application
CN104231592B (en) * 2014-09-12 2017-02-15 美瑞新材料股份有限公司 Foaming type thermoplastic polyurethane particles and preparation method thereof
CN105218851A (en) * 2015-09-08 2016-01-06 宁波大学 A kind of method preparing polymkeric substance hole-opening foaming material
CN106084447B (en) * 2016-05-13 2018-08-14 宁波大学 A kind of thermal plastic high polymer composition open-cell foaming material and preparation method thereof
CN106084448B (en) * 2016-05-13 2018-08-17 宁波大学 A kind of thermal plastic high polymer composition inierpeneirating network structure and preparation method thereof
CN109354861B (en) * 2017-08-04 2021-06-08 南通德亿新材料有限公司 Thermoplastic micro-balloon polymer elastomer material and preparation method thereof
CN109320951B (en) * 2017-08-04 2021-06-08 南通德亿新材料有限公司 Degradable antifouling thermoplastic micro-balloon polymer elastomer material and preparation method thereof
CN107298848B (en) * 2017-08-04 2019-01-18 南通德亿新材料有限公司 A kind of micro- air bag polyurethane elastomer material of particle diameter thermoplasticity and preparation method thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101245159A (en) * 2008-03-28 2008-08-20 天津市润达塑料包装有限公司 Process for manufacturing polyolefin foaming particle material
CN102056967A (en) * 2008-06-12 2011-05-11 3A科技和管理有限公司 Foamed polyesters and methods for their production
CN105592997A (en) * 2013-08-16 2016-05-18 比瑞塑料公司 Polymeric material for an insulated container
CN103709726A (en) * 2013-12-17 2014-04-09 烟台开发区新龙华包装材料有限公司 Extrusion foaming thermoplastic polyurethane elastomer bead and preparation method thereof
CN103804890A (en) * 2014-02-18 2014-05-21 山东美瑞新材料有限公司 Extruded foaming thermoplastic polyurethane elastomer particles and preparation method thereof
CN104974370A (en) * 2015-01-19 2015-10-14 常州市顺祥新材料科技有限公司 Preparation method of thermoplastic polyurethane beads and bead molding technology
CN104877335A (en) * 2015-05-06 2015-09-02 丁钰 Thermoplastic polyurethane elastomer foamed bead and preparation method thereof
CN106541508A (en) * 2016-08-19 2017-03-29 浙江佳阳塑胶新材料有限公司 A kind of method that endothermic blowing agent prepares expanded bead with reference to supercritical nitrogen

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019024869A1 (en) * 2017-08-04 2019-02-07 南通德亿新材料有限公司 Degradable antifouling thermoplastic micro-airbag polymer elastomer material and preparation therefor
WO2019024588A1 (en) * 2017-08-04 2019-02-07 南通德亿新材料有限公司 Degradable antifouling thermoplastic micro-airbag polymer elastomer material and preparation thereof
WO2019024868A1 (en) * 2017-08-04 2019-02-07 南通德亿新材料有限公司 Thermoplastic micro-sac polymer elastomer material and preparation method therefor
WO2019024870A1 (en) * 2017-08-04 2019-02-07 南通德亿新材料有限公司 Micro-particle-size thermoplastic micro-airbag polyurethane elastomer material and preparation therefor
CN107722602A (en) * 2017-09-26 2018-02-23 上海德亿化工有限公司 Foamed profile of Memorability multiple spot positive feedback resilient material and preparation method thereof
CN107746570A (en) * 2017-09-26 2018-03-02 上海德亿化工有限公司 A kind of polyamide expanded material its preparation method
CN108864662A (en) * 2018-07-25 2018-11-23 南通德亿新材料有限公司 A kind of thermoplastic polyether ester elastomer foamed material and preparation method thereof
CN108864662B (en) * 2018-07-25 2020-10-13 南通德亿新材料有限公司 Thermoplastic polyether ester elastomer foam material and preparation method thereof
CN109228003A (en) * 2018-09-19 2019-01-18 福建鑫瑞新材料科技有限公司 A kind of device and method preparing low-density polymeric foam beads using overcritical fluid-mixing extrusion foaming

Also Published As

Publication number Publication date
CN107446343B (en) 2019-03-08
CN109320951A (en) 2019-02-12
WO2019024869A1 (en) 2019-02-07
WO2019024588A1 (en) 2019-02-07
CN109320951B (en) 2021-06-08

Similar Documents

Publication Publication Date Title
CN107446343B (en) A kind of micro- balloon polymer elastomeric material of degradable antifouling thermoplasticity and its preparation
CN107298847B (en) A kind of micro- balloon polymer elastomeric material of thermoplasticity and preparation method thereof
CN107298848B (en) A kind of micro- air bag polyurethane elastomer material of particle diameter thermoplasticity and preparation method thereof
CN107383854B (en) A kind of preparation method of the micro- air bag elastomeric material of thermoplastic polyurethane
CN109206892B (en) High-elasticity foamed shoe midsole material and preparation method and application thereof
CN107722602A (en) Foamed profile of Memorability multiple spot positive feedback resilient material and preparation method thereof
JP3266272B2 (en) Biodegradable filter material and method for producing the same
EP1102814A1 (en) Film containing starch or starch derivatives and polyester urethanes
CN106905636A (en) The polyvinyl chloride resin wood-plastic decorating material and its manufacture method of adsorbable gas formaldehyde
CN107746570A (en) A kind of polyamide expanded material its preparation method
CN108059806A (en) A kind of 3D printing PLA/TPU composite materials
CN1919926A (en) Polylactic acid-starch foaming material and preparation method thereof
CN104513430B (en) A kind of rattan imitating PP foam material and preparation method thereof
Park et al. Axiomatic design of a microcellular filament extrusion system
CN106674997A (en) Foamed TPU (Thermoplastic polyurethane) material and foaming process thereof
CN106751684A (en) A kind of fragrance type, low distribute Polycarbonate alloy material and preparation method thereof
CN113563627B (en) Controllable lightweight foam material for FDM printing and preparation method and application thereof
CN107501750A (en) Composite and preparation method thereof and air-conditioning product
DE2142855C3 (en) Process for the production of molded articles from plastic
CN107987458A (en) It is a kind of suitable for plastics of 3D printing and preparation method thereof
US11912843B2 (en) Recyclable, biodegradable, and industrially compostable extruded foams, and methods of manufacturing the same
AU771136B2 (en) Method for forming an article comprising closed-cell microfoam from thermoplastic
CN116607244A (en) Parallel composite self-curling polyester staple fiber with regenerated polyester as raw material, preparation method and system
DE19900489A1 (en) Process for the production of loadable plastic foams
RU2398791C1 (en) Method of preparing polystyrene granulate capable of foaming

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant