CN108440783A - A kind of polyurethane foam bead and preparation method thereof - Google Patents
A kind of polyurethane foam bead and preparation method thereof Download PDFInfo
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- CN108440783A CN108440783A CN201810391494.9A CN201810391494A CN108440783A CN 108440783 A CN108440783 A CN 108440783A CN 201810391494 A CN201810391494 A CN 201810391494A CN 108440783 A CN108440783 A CN 108440783A
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- 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
- C08J9/16—Making expandable particles
- C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- 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
- C08J9/22—After-treatment of expandable particles; Forming foamed products
- C08J9/228—Forming foamed products
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- 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
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- 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
Abstract
The invention discloses polyurethane foam beads and preparation method thereof, are related to expanded material technical field.One specific implementation mode of the polyurethane foam bead includes：By weight, 0.1~1.5 part of 25~40 parts of MDI, 6~12 parts of chain extender, 55~70 parts of polyalcohol, 1~5 part of nucleating agent, 2~5 parts of foaming agent, 0.1~0.8 part of antioxidant and anti-yellowing additives.Polyurethane foam bead provided in an embodiment of the present invention and preparation method thereof, obtained polyurethane foam bead has extremely low density, excellent resilience and wearability, and the stability of properties is good.
Description
Technical field
The present invention relates to expanded material technical fields more particularly to a kind of polyurethane foam bead and preparation method thereof.
Background technology
Polyurethane have excellent wearability, chemical resistance, high resiliency and be applied to footwear material.Polyurethane foam material
Not only have many advantages, such as the above-mentioned of polyurethane resin, also there is lightweight, softness, high rebound, therefore be used for novel high property
It can sport footwear footwear material field.
Patent document WO2010/136398A, CN102229709A, CN103642200A, CN103951965A disclose with
Physical blowing agent, the method for preparing polyurethane foam material by kettle pressure or moulded from foam technique, this method is not using friendship
Join agent, prepared expanded material has the advantage of fusible recycling processing.But, this method is batch-foamed process, is existed
Processing efficiency is low and the unstable problem of properties of product batch.Secondly, polyurethane resin is related at long-time boiling water in this method
Reason easily leads to polyurethane resin and chemical degradation and xanthochromia problem occurs, and affects the performance of polyurethane foam material and subsequently makes
With.
Patent document CN102276785A, CN103183805A disclose continuous extrusion molding and prepare polyurethane foam material
Method, this method by reaction monomers, catalyst, crosslinking agent, the components such as sulphur agent, foaming agent is helped to be mixed according to certain mode, pass through
Reaction monomers polymerization, foaming agent decompose, and form polymer/gas melt, are most prepared into polyurethane foam grain through granulation underwater afterwards
Sub- material.The melt strength of polyurethane resin is relatively low, continuous to squeeze out prepared expanded material and ask there are open cell content is excessively high
Topic, causes expanded particle to be difficult to carry out vapor compression molding, to prepare the material being suitable for the application of.It is handed over by strand
Join to improve melt strength, the appearance of strand cross-linked structure reduces the melting recycling ability of polyurethane foam material.In addition,
Since that there are tolerance is low, be hard to be uniformly dispersed in polyurethane matrix, be difficult to decompose completely, contains solid decomposition for chemical foaming agent
Object, foaming agent and solid decomposer contain color, and density, the abscess shape of polyurethane foam material will be influenced using chemical foaming agent
The color of state and product.
Patent document WO2007/082838A, which is disclosed, uses aliphatic saturated hydrocarbon for foaming agent, continuous to squeeze out granulation underwater system
The method of standby polyurethane foam particle.Fragrant hydrocarbon blowing agent used is odorous and easily burns, and there are environmental issues and production
Safety problem.In addition, since polyurethane resin melt strength is low, prepared polyurethane foam material there is also percent opening height,
Easily there is the high problem of shrink of product rate in polyurethane foam particle vapor forming process.
Patent document WO2002/4628A is described prepares high density using high-pressure fluid or supercritical fluid as foaming agent
The method of polyurethane foam material.The hardness of polyurethane foam material prepared by this method is not less than shore hardness in 90A.It is this
Polyurethane foam material is mainly used in the polishing pad of semiconductor crystal wafer, and is unsuitable for preparing the sport footwear buffering shoe of soft
Material.
Invention content
In view of this, a kind of polyurethane foam bead of offer of the embodiment of the present invention and preparation method thereof, obtained polyurethane
Expanded bead has extremely low density, excellent resilience and wearability, and the stability of properties is good.
To achieve the above object, one side according to the ... of the embodiment of the present invention provides a kind of polyurethane foam bead.
Polyurethane foam bead according to the ... of the embodiment of the present invention, by weight, including：
25~40 parts of MDI, 6~12 parts of chain extender, 55~70 parts of polyalcohol, 1~5 part of nucleating agent, 2~5 parts of foaming agent,
0.1~1.5 part of 0.1~0.8 part of antioxidant and anti-yellowing additives.
Optionally, the polyalcohol is the copolymerization product of polytetrahydrofuran ether or caprolactone and tetrahydrofuran, described polynary
The molecular weight of alcohol is 800~3500.
Optionally, the chain extender includes following at least one：1,4- butanediols, 1,3- propylene glycol and diethylene glycol.
Optionally, the nucleating agent includes following at least one：Superfine silicon dioxide, calcium carbonate superfine powder, the nucleating agent
Grain size be 2000~3000 mesh；The foaming agent includes following at least one：Liquid carbon dioxide, nitrogen.
Optionally, the antioxidant includes following at least one：1010、245；The anti-yellowing additives are ultraviolet absorber
531 and light stabilizer 944 equal proportion by weight be mixed to get.
Another aspect according to the ... of the embodiment of the present invention provides the polyurethane hair of first aspect of embodiment of the present invention offer
Steep the preparation method of bead.
The preparation method of polyurethane foam bead according to the ... of the embodiment of the present invention, including：
Step S1, the synthesis of polyurethane particles：Chain extender, polyalcohol, antioxidant and anti-yellowing additives are pre-mixed
Uniformly, MDI is added, is uniformly mixed, is cured 15~20 minutes at a temperature of 120~160 DEG C, cutting crushing after cooling is gathered
Urethane particle；
Step S2, the production of expanded bead：Polyurethane particles are plasticized using plasticizing apparatus, are filled respectively by the plasticizing
Nucleating agent and foaming agent is added in the different spouts set；Polyurethane foam bead is obtained by pelletizing mode in water.
Optionally, in step S2, the plasticizing apparatus is parallel equidirectional two-screw equipment, the parallel equidirectional two-screw
Draw ratio is 40~60, has 1~4 side spout.
Optionally, in step S1, for the shore hardness of polyurethane between 85~92A, rebound value is more than 45% after curing,
DIN abrasion are less than 40mm3。
Optionally, in step S2, the nucleating agent is added by weight-loss metering mode in the plasticizing apparatus；The foaming
Agent includes following at least one：Liquid carbon dioxide, nitrogen, liquid CO 2 are added the plasticizing using high-pressure plunger pump and fill
In setting, nitrogen is added using booster pump and pressure maintaining valve constant pressure in the plasticizing apparatus.
Optionally, in step S2, pelletizing mode uses electromagnetic heating, template to use diamond and metal in the water
Agglomerated material machine-shaping.
Further effect possessed by above-mentioned non-usual optional mode adds hereinafter in conjunction with specific implementation mode
With explanation.
Specific implementation mode
Below to the present invention exemplary embodiment explain, including the embodiment of the present invention various details to help
In understanding, they should be thought only exemplary.Therefore, it will be appreciated by those of ordinary skill in the art that, can be right
The embodiments described herein makes various changes and modifications, without departing from scope and spirit of the present invention.Equally, in order to clear
And simplicity, the description to known function and structure is omitted in following description.
One side according to the ... of the embodiment of the present invention provides a kind of polyurethane foam bead.
Polyurethane foam bead according to the ... of the embodiment of the present invention, including：MDI, chain extender, polyalcohol, nucleating agent, foaming
Agent, antioxidant and anti-yellowing additives.
MDI is 4,4'- methyl diphenylene diisocyanates (also known as pure MDI), more containing the pure MDI of certain proportion and more phenyl
The modifier (also known as modified MDI) of the mixture (also known as polymeric MDI) of methylene polyisocyanates and pure MDI and polymeric MDI
General name.The polyurethane produced using MDI, the elasticity of existing rubber, and have the intensity of plastics and excellent processing performance, especially
It is to have the advantages that other synthetic materials are incomparable in heat-insulated, sound insulation, wear-resisting, oil resistant, elasticity etc..In optional embodiment
In, MDI used is pure MDI, i.e. 4,4'- methyl diphenylene diisocyanates.
MDI has influence to the hardness of polyurethane foam bead obtained.The content of MDI is more, polyurethane hair obtained
The hardness for steeping bead is bigger.By taking producing sole material especially sport shoe sole material as an example, the hardness of polyurethane foam bead
Too big, material for sole of shoe is harder, and comfort is poor；The hardness of polyurethane foam bead is too small, then is difficult to be molded, and is unfavorable for producing shoes
Bottom.Based on this, by weight, the content of MDI could be provided as 25~40 parts in polyurethane foam bead.
Chain extender is also known as chain extender, be can with the functional group reactions on linear polymer chain and make strand extension, point
Son measures increased substance.The content of chain extender has not significant impact the resilience of polyurethane foam bead obtained, but right
The wearability and molding effect of polyurethane foam bead obtained have influence.In the embodiment of the present invention, by weight, polyurethane
The content of chain extender is 6~12 parts in expanded bead.The content of chain extender is properly increased, the wear-resisting of polyurethane foam bead is corresponded to
Property is slightly good.The content of chain extender is higher, and the hardness of polyurethane foam bead is bigger, and making sole is should not be used in when hardness is too big
Material.If the content of chain extender is relatively low, the fusing point for corresponding to polyurethane foam bead is relatively low, it is difficult to be molded.Further, this hair
Chain extender in bright embodiment is the small molecule chain extender that molecular weight is not more than 210.
Chain extender may include following at least one：1,4- butanediols, 1,3- propylene glycol and diethylene glycol.Practical application mistake
Cheng Zhong may be used any one of the above, use with as chain extender for two or three.Due to often mostly using a kind of component, just need
Increase the metering device of corresponding component.It, can be only with it in order to reduce the complexity and manufacturing cost of production process as possible
In any one or both be used as chain extender.Using above-mentioned chain extender, it is strong on the one hand raising melt can be crosslinked by strand
Degree, and then resilience, the wearability of polyurethane foam bead are improved, on the other hand also ensure that the melting of polyurethane foam bead is returned
Receipts ability.
Alcohols containing two or more hydroxyls in polyalcohol, that is, molecule.In the embodiment of the present invention, by weight, gather
The content of polyalcohol is 55~70 parts in urethane expanded bead.The content of polyalcohol is higher, and the hardness of polyurethane foam bead is got over
It is small, fusing point is lower, it is difficult to be molded.The content of polyalcohol is lower, and the hardness of polyurethane foam bead is bigger, not when hardness is too big
It is preferably used to make material for sole of shoe.
In some optional embodiments, polyalcohol is the copolymerization production of polytetrahydrofuran ether or caprolactone and tetrahydrofuran
The molecular weight of object, polyalcohol is 800~3500.The molecular weight of polyalcohol has shadow to the flexibility that polyurethane foam bead is made
It rings, molecular weight is bigger, and it is more soft that polyurethane foam bead is made.On the one hand, it is more soft that polyurethane foam bead is made, is given birth to this
The sole of production is more comfortable, but too soft, and sole wears no resistance.Using the polyalcohol of the present embodiment, polyurethane can be taken into account
Wearability, hardness, resilience and the density of expanded bead.
Nucleating agent is capable of the crystallization behavior of feed change, accelerates crystalline rate, increases crystal density and promote crystallite dimension
Miniaturization reaches and shortens molding cycle, improve product surface gloss, tensile strength, rigidity, heat distortion temperature, impact resistance, resist
The effect of the physical mechanical properties such as creep properties.In the embodiment of the present invention, by weight, nucleating agent contains in polyurethane foam bead
Amount is 1~5 part.When the content of nucleating agent is too low, the effect for changing crystallization behavior can not be effectively played；The too high levels of nucleating agent
When, it is easily destroyed the intensity of polyurethane foam bead so that the resilience and wearability of polyurethane foam bead are poor.
In an alternate embodiment of the invention, nucleating agent includes following at least one：Superfine silicon dioxide, calcium carbonate superfine powder, nucleation
The grain size of agent is 2000~3000 mesh.The grain size of nucleating agent is too small, then is difficult to be dispersed in other raw materials；The grain size of nucleating agent is too
Greatly, then the grain size that polyurethane foam bead is made is too big, and structural homogeneity is poor.In addition, adding two in polyurethane foam bead
Silica can also improve the wearability and resilience of polyurethane foam bead；Ultra-fine carbon is added in polyurethane foam bead
Sour calcium can also increase polyurethane foam bead volume, reduce cost, improve polyurethane foam bead hardness, wearability and steady
It is qualitative.
Foaming agent is the substance for making object substance pore-forming.In the embodiment of the present invention, by weight, in polyurethane foam bead
The content of foaming agent is 2~5 parts.The content of foaming agent has influence, the content of foaming agent to the density of polyurethane foam bead
Too low, the density of polyurethane foam bead is too big, does not reach requirement density；The content of foaming agent is too high, then can not dissolve in poly- ammonia
Other raw materials of ester foaming bead.In some embodiments, foaming agent may include following at least one：Liquid carbon dioxide,
Nitrogen.It is environmentally protective using this foaming agent, on the one hand do not interfere with density, cell morphology and the face of polyurethane foam bead
Color；On the other hand it can be dispersed in the material system of polyurethane foam bead, and foaming power and foam stability are good, greatly
It is big to improve gained polyurethane foam bead properties and its stability.
Antioxidant is to prevent the dysgenic substance of oxygen.Antioxidant is added in the embodiment of the present invention can prevent from gathering
Urethane expanded bead is aoxidized or is occurred xanthochromia, prevent due to aoxidized or occurred xanthochromia to the performance of polyurethane foam bead with
And the harmful effect subsequently used.By weight, the content of antioxidant is 0.1~0.8 part in polyurethane foam bead.Antioxygen
The content of agent is too low, then can not effectively play antioxidant effect；The too high levels of antioxidant can increase polyurethane foam pearl
The production cost of grain.In some embodiments, antioxidant may include following at least one：1010, chemistry is entitled：Four [β-
(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, CAS numbers are 633-85-74；245, i.e., it is a kind of especially suitable
For the three-dimensional Hinered phenols antioxidant of organic polymer, CAS numbers are 31570-04-4.
Addition anti-yellowing additives can prevent polyurethane foam bead from xanthochromia occurs.In the embodiment of the present invention, by weight,
The content of anti-yellowing additives is 0.1~1.5 part in polyurethane foam bead.The too high levels of anti-yellowing additives can increase poly- ammonia
The production cost of ester foaming bead；The content of anti-yellowing additives is too low, then can not effectively play yellowing-resistant effect.Of the invention real
It is anti-yellowing when the content of anti-yellowing additives is 0.5~1.0 part in the material system that the polyurethane foam bead of example offer is provided
Become effect most.In some optional embodiments, anti-yellowing additives be ultraviolet absorber 531 and light stabilizer 944 by weight etc.
What ratio was mixed to get.The Chinese nickname of ultraviolet absorber 531 is：[2- hydroxyls -4- (octyloxy) phenyl] phenyl ketone, CAS are compiled
Number be 1843-05-6.Light stabilizer 944 also known as hindered amine light stabilizer HS-944, CAS number are 70624-18-9,71878-
19-8。
Another aspect according to the ... of the embodiment of the present invention provides the preparation method of above-mentioned polyurethane foam bead.
The preparation method of polyurethane foam bead according to the ... of the embodiment of the present invention, including：
Step S1, the synthesis of polyurethane particles：Chain extender, polyalcohol, antioxidant and anti-yellowing additives are pre-mixed
Uniformly, MDI is added, is uniformly mixed, is cured 15~20 minutes at a temperature of 120~160 DEG C, cutting crushing after cooling is gathered
Urethane particle；
Step S2, the production of expanded bead：Polyurethane particles are plasticized using plasticizing apparatus, are filled respectively by the plasticizing
Nucleating agent and foaming agent is added in the different spouts set；Polyurethane foam bead is obtained by pelletizing mode in water.
Plasticizing apparatus in step S2 can be parallel equidirectional two-screw equipment.The draw ratio of parallel equidirectional two-screw can be with
Selection setting is carried out according to actual conditions, such as is set as 40~60.The spout quantity of parallel equidirectional two-screw can also root
It is configured according to needs of production, for example, 1~4 side spout of setting.Feeding is carried out using more spouts so that former
The good mixing effect of material, stability, wearability, resilience and the hardness that polyurethane foam bead is made are high.
In order to further increase each performance of polyurethane foam bead, the shore hardness of polyurethane after being cured in step S1
It can control between 85~92A, rebound value is more than 45%, DIN abrasion and is less than 40mm3.Rebound refers to object under force
Physical deformation is generated, when pressure is released generated reduction or the physical change of the state closely restored；Rebound value refers to working as pressure
When power discharges, the ratio between the snap-off-distance of polyurethane foam bead and size before deforming.Abrasion are that reflection is wear-resisting
Property an index, DIN abrasion be using DIN (be Germany standardization competent authority, as national standardizing body participate in
The non-governmental characteristics standardizing body of international and regional) abrasion machine measure wearing valve, specific testing procedure is referring to concerned countries
Standard, details are not described herein again.
The shore hardness of polyurethane controls between 85~92A after curing, rebound value is more than 45%, DIN abrasion and is less than
40mm3, enable to polyurethane foam bead obtained that there is extremely low density, excellent resilience and wearability, later stage to add
Work process stabilizing.
Nucleating agent can be added by weight-loss metering mode in plasticizing apparatus in step S2.Weight-loss metering is according to the unit interval
The decrement Continuous plus that interior feed bin weighs goes out the number of inventory, and according to the setting value of inventory size and inventory
Comparison result controls adjustment delivery rate, to making inventory be consistent with its setting value.
When using liquid carbon dioxide and/or nitrogen as foaming agent, liquid CO 2 can use high-pressure plunger
Pump is added in plasticizing apparatus, and nitrogen can use booster pump and pressure maintaining valve constant pressure to be added in the plasticizing apparatus.Added using this
Material mode can accurately control charging rate and feeding quantity, ensure that foaming agent is uniformly mixed with other components, improve polyurethane hair
Steep the particle uniformity of bead.
Electromagnetic heating may be used in pelletizing mode in water in step S2.By the way of electromagnetic heating, heating speed is fast,
Warm temperature is accurately controllable.The template of pelletizing can use the agglomerated material machine-shaping of diamond and metal in water.Use gold
The agglomerated material of hard rock and metal is processed, and hardness is high, and wearability is good.
The preparation method of the present invention is illustrated below in conjunction with specific embodiment.
The preparation method of polyurethane foam bead, includes the following steps：
The synthesis of S1, polyurethane particles：By weight, by 6~12 parts of small molecule chain extender, polyalcohol (adopt by the present embodiment
Polyalcohol is the copolymerization product of polytetrahydrofuran ether or caprolactone and tetrahydrofuran) 55~60 parts, antioxidant 0.1~
0.8 part is pre-mixed uniformly with 0.5~1.5 part of anti-yellowing additives, adds 25~40 parts of pure MDI, is mixed using casting machine equal
It is even, it is cured 15~20 minutes in 120~160 degree of tunnel ovens, it is irregular granules that crushing is cut after cooling, obtains polyurethane
Grain, control the shore hardnesses of polyurethane particles between 85~92A, rebound value is more than 45%, DIN abrasion and is less than 40mm3；
The production of S2, expanded bead：Polyurethane particles raw material is plasticized using parallel equidirectional two-screw, passes through first side
1~12 part of nucleating agent is added by weight-loss metering mode in spout, and liquid CO 2 is added by the second third side spout
And nitrogen.Wherein, liquid CO 2 is added in parallel equidirectional two-screw using high-pressure plunger pump, and passes through mass flowmenter
Control addition each second；Nitrogen constant pressure is added in parallel equidirectional two-screw using booster pump and pressure maintaining valve.By being cut in water
Grain mode obtains polyurethane foam bead.
The embodiment of the present invention uses parallel equidirectional two-screw extruder and one or more foaming agents is added to survey feeding manner
Continuous production polyurethane foam bead.Obtained polyurethane foam bead has extremely low density, excellent rebound and wearability
Can, post-production process stabilizing.
Above-mentioned specific implementation mode, does not constitute limiting the scope of the invention.Those skilled in the art should be bright
It is white, design requirement and other factors are depended on, various modifications, combination, sub-portfolio and replacement can occur.It is any
Modifications, equivalent substitutions and improvements made by within the spirit and principles in the present invention etc., should be included in the scope of the present invention
Within.
Claims (10)
1. a kind of polyurethane foam bead, which is characterized in that by weight, including：
25~40 parts of MDI, 6~12 parts of chain extender, 55~70 parts of polyalcohol, 1~5 part of nucleating agent, 2~5 parts of foaming agent, antioxygen
0.1~1.5 part of 0.1~0.8 part of agent and anti-yellowing additives.
2. polyurethane foam bead as described in claim 1, which is characterized in that the polyalcohol be polytetrahydrofuran ether or oneself
The molecular weight of the copolymerization product of lactone and tetrahydrofuran, the polyalcohol is 800~3500.
3. polyurethane foam bead as described in claim 1, which is characterized in that the chain extender includes following at least one：
1,4- butanediols, 1,3- propylene glycol and diethylene glycol.
4. polyurethane foam bead as described in claim 1, which is characterized in that the nucleating agent includes following at least one：
The grain size of superfine silicon dioxide, calcium carbonate superfine powder, the nucleating agent is 2000~3000 mesh；The foaming agent include it is following at least
It is a kind of：Liquid carbon dioxide, nitrogen.
5. polyurethane foam bead according to claim 1, which is characterized in that the antioxidant includes following at least one
Kind：1010、245；The anti-yellowing additives are that ultraviolet absorber 531 and the equal proportion by weight of light stabilizer 944 are mixed to get.
6. the preparation method of the polyurethane foam bead as described in Claims 1 to 5 is any, which is characterized in that including：
Step S1, the synthesis of polyurethane particles：Chain extender, polyalcohol, antioxidant and anti-yellowing additives are pre-mixed uniformly,
MDI is added, is uniformly mixed, is cured 15~20 minutes at a temperature of 120~160 DEG C, cutting crushing after cooling obtains polyurethane
Particle；
Step S2, the production of expanded bead：Polyurethane particles are plasticized using plasticizing apparatus, pass through the plasticizing apparatus respectively
Nucleating agent and foaming agent is added in different spouts；Polyurethane foam bead is obtained by pelletizing mode in water.
7. preparation method as claimed in claim 6, which is characterized in that in step S2, the plasticizing apparatus is parallel double in the same direction
The draw ratio of screw apparatus, the parallel equidirectional two-screw is 40~60, has 1~4 side spout.
8. preparation method as claimed in claim 6, which is characterized in that in step S1, the shore hardness of polyurethane exists after curing
Between 85~92A, rebound value is more than 45%, DIN abrasion and is less than 40mm3。
9. preparation method according to claim 6, which is characterized in that in step S2, the nucleating agent passes through weight-loss metering
Mode is added in the plasticizing apparatus；The foaming agent includes following at least one：Liquid carbon dioxide, nitrogen, liquid dioxy
Change carbon to be added in the plasticizing apparatus using high-pressure plunger pump, nitrogen is added the plasticizing using booster pump and pressure maintaining valve constant pressure and fills
In setting.
10. preparation method according to claim 6, which is characterized in that in step S2, pelletizing mode is using electricity in the water
Magnetic heats, and template uses the agglomerated material machine-shaping of diamond and metal.
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Effective date of registration: 20181225 Address after: 351131 Dongchuan Road, Licheng District, Putian City, Fujian Province Applicant after: Fujian Putian Liansheng Shoes Co., Ltd. Address before: 351100 Xiadian Road, Gongchen Street, Licheng District, Putian City, Fujian Province, 298 Applicant before: Putian Licheng District Chuang Hong shoe industry information consulting center (limited partnership) |
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