CN105694430A - Tpu foaming material and preparation method thereof - Google Patents

Tpu foaming material and preparation method thereof Download PDF

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Publication number
CN105694430A
CN105694430A CN201610124645.5A CN201610124645A CN105694430A CN 105694430 A CN105694430 A CN 105694430A CN 201610124645 A CN201610124645 A CN 201610124645A CN 105694430 A CN105694430 A CN 105694430A
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parts
raw material
tpu
foaming
thermoplastic polyurethane
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CN105694430B (en
Inventor
吴启超
黎华强
莫梓健
杨鹏
徐加鹏
沈永琪
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Anhui Tian'an New Materials Co Ltd
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Anhui Tian'an New Materials Co Ltd
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C08J9/06—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 chemical blowing agent
    • C08J9/08—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 chemical blowing agent developing carbon dioxide
    • 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
    • C08J9/06—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 chemical blowing agent
    • C08J9/10—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 chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • 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
    • C08J9/06—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 chemical blowing agent
    • C08J9/10—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 chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
    • C08J9/105—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof containing sulfur
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0278—Polyurethane
    • 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
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • 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
    • 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
    • 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
    • C08L2312/00—Crosslinking

Abstract

The invention discloses a TPU foaming material and a preparation method thereof. The TPU foaming material is prepared from, by weight, 100 parts of thermoplastic polyurethane, 1-10 parts of a foaming agent and 3-30 parts of hot melt glue. The shore hardness of the thermoplastic polyurethane is 45A-50D, and polyurethane hot melt glue which can be cured in moisture is adopted as the hot melt glue. The preparation method of the TPU foaming material includes the following steps that firstly, after the raw materials are mixed, a TPU membrane or a sheet is produced through a calendaring molding method or an extrusion molding method; secondly, the TPU membrane or the sheet is placed for 0.5-5 days at the temperature of 15-55 DEG C under the condition that humidity is 65% or above, and moisture curing is performed; thirdly, the TPU membrane or the sheet subjected to moisture curing is heated for foaming, and the finished product is obtained.

Description

TPU expanded material and preparation method thereof
Technical field
The present invention relates to a kind of polymeric material field, particularly to TPU expanded material and preparation method thereof。
Background technology
TPU (Polyurethane Thermoplastic Elastomer) is the family macromolecule material between rubber and plastics, it has the feature of its hardness range width, wear-resisting, oil resistant, transparent, good springiness, its resistance to ag(e)ing is better than rubber, wearability, resilience force are all better than heat-curable urethane and PVC, are the optimal materials substituting PVC and PU。Prior art obtains low-density microcellular polyurethane elastomer, alternative rubber and PVC frequently with heat-curable urethane and makes sole。But this technique manufacturing process is seriously polluted, and the strength of materials is low, production cost is high。Prior art also there is the method adopting dynamic crosslinking make TPU foam films, the method is a kind of work two kinds Polyurethane Thermoplastic Elastomer added in cross-linking agent such as dual-tert-butyl cumene hydroperoxide and cumyl peroxide and adds and carry out foaming after some auxiliary agents carry out mixing slice again and obtain expanded material, this expanded material product quality is difficult to control to, easily occur that abscess is thick, the defect that lack of homogeneity, toughness are low。
Summary of the invention
It is an object of the invention to provide TPU expanded material that a kind of abscess is tiny, uniformity good, toughness is high and preparation method thereof。
According to an aspect of the invention, it is provided TPU expanded material, the following component including with parts by weight: thermoplastic polyurethane 100 parts, foaming agent 1～10 part and PUR 3～30 parts。
The shore hardness of above-mentioned thermoplastic polyurethane is 45A～50D, and PUR adopts moisture cured polyurethane hot melt。
The preparation method of above-mentioned TPU expanded material, comprises the steps:
1) by after mixing for raw material and adopt rolling-molding method or extrusion moulding to produce TPU membrane or sheet material；
2) by step 1) TPU membrane that produces or sheet material be that 15～55 DEG C of humidity condition more than 65% is transferred and set to 0 .5～5 day in temperature, carries out moisture-curable。
3) TPU membrane after moisture-curable or sheet material are heated foam, obtain finished product。
In some embodiments, step 1) calendering formation temperature at 115～150 DEG C。
In some embodiments, step 3) blowing temperature be 170～230 DEG C。
In some embodiments, step 1) in the manufacturing process of rolling-molding method as follows:
A, other foaming layer raw material beyond heat extraction melten gel is put in blender stirring mixing；
B, mixed for stirring raw material is sent in the lump together with PUR banbury carries out banburying；
C, raw material banburying completed are sent in mill and are carried out out refining；
D, open refining after raw material be re-fed in calender to carry out calendering formation after filtering。
The invention has the beneficial effects as follows: by by after mixing for the raw material of TPU expanded material and adopt rolling-molding method or extrusion moulding to produce to roll and TPU membrane or sheet material, then TPU membrane or sheet material are placed 0.5～5 day, carry out moisture-curable。Finally the TPU membrane after moisture-curable or sheet material are heated and foam, obtain finished product。Moisture cured polyurethane hot melt joins in raw material and uses as cross-linking agent, place a couple of days after calendering or extrusion molding, before foaming, TPU membrane or sheet material are carried out moisture-curable, make the internal material generating section crosslinking curing of TPU membrane or sheet material, TPU melt strength can be improved, can avoid producing excessive and uneven abscess when foaming, improve the uniformity of foam bubble and the toughness of material。
According to another aspect of the present invention, it is provided that TPU expanded material, including the surface layer being sequentially connected with, foaming layer and bottom fabricbase, wherein,
The raw material making surface layer includes the following component with parts by weight: thermoplastic polyurethane 100 parts；
The raw material making foaming layer includes the following component with parts by weight: thermoplastic polyurethane 100 parts, foaming agent 1～10 part, PUR 3～30 parts；
The shore hardness of above-mentioned thermoplastic polyurethane is 45A～50D。Bottom fabricbase can be looped fabric, woven fabric or non-woven fabrics。PUR adopts moisture cured polyurethane hot melt。
In some embodiments, the raw material making surface layer can also include the following component with parts by weight: 0.1～2 part of antioxidant, ultraviolet (UV) resistant agent 0.1～4 part and fire retardant 1～20 part。
In some embodiments, the raw-material optimum ratio making surface layer is include the following component with parts by weight: thermoplastic polyurethane 100 parts, 0.5～1 part of antioxidant, ultraviolet (UV) resistant agent 0.5～2 part and fire retardant 5～13 parts。
In some embodiments, the raw material making foaming layer can also include 0.1～2 part of the antioxidant with parts by weight and fire retardant 5～50 parts。
In some embodiments, the raw-material optimum ratio making foaming layer is include the following component with parts by weight: thermoplastic polyurethane 100 parts, foaming agent 3～6 parts, PUR 10～20 parts, 0.5～1 part of antioxidant and fire retardant 5～13 parts。
Antioxidant can be preferably antioxidant 1010 (four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester), antioxidant 1076 (β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid octadecanol ester), antioxidant 245 (triethylene glycol ether-two (3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester), one or more mixing in irgasfos 168 (three [2.4-di-tert-butyl-phenyl] phosphite ester) and antioxidant DDPP (diphenylisodecyl base ester)。Antioxidant may be used without other antioxidant commonly used in the art。
Ultraviolet (UV) resistant agent can be preferably one or more mixing in benzotriazole, benzophenone, triazine。Ultraviolet (UV) resistant agent may be used without other ultraviolet (UV) resistant agent commonly used in the art。
Fire retardant adopts halogen-free flame retardants。Thus, halogen-free flame retardants will not decompose generation harmful gas when being subject to high temperature, can avoid secondary pollution。
Foaming agent can be preferably one or more in azodicarbonamide, 4,4-OBSH, p-toluene sulfonylsemicarbazide and sodium bicarbonate。Foaming agent may be used without other foaming agent commonly used in the art。
The preparation method of above-mentioned TPU expanded material, comprises the steps:
1) by after mixing for foaming layer raw material and adopt rolling-molding method or extrusion moulding to produce foaming layer, the foaming layer of calendering or extrusion is fitted with bottom fabricbase while hot；
2) by after mixing for foaming layer raw material and adopt rolling-molding method or extrusion moulding to produce surface layer, the surface layer of calendering or extrusion obtains TPU membrane or sheet material with foaming layer laminating while hot；
3) by step 2) TPU membrane that obtains or sheet material be that 15～55 DEG C of humidity condition more than 65% is transferred and set to 0 .5～5 day in temperature, carries out moisture-curable。
4) TPU membrane after moisture-curable or sheet material are heated to 170～230 DEG C and foam, obtain finished product。
Above-mentioned steps 1) and step 2) calendering formation temperature at 115～150 DEG C。
Step 1) in by after mixing for foaming layer raw material and adopt rolling-molding method to produce to roll the manufacturing process foaming layer as follows:
A, other foaming layer raw material beyond heat extraction melten gel is put in blender stirring mixing；
B, mixed for stirring raw material is sent in the lump together with PUR banbury carries out banburying；
C, raw material banburying completed are sent in mill and are carried out out refining；
D, open refining after raw material be re-fed in calender to carry out calendering formation after filtering。
Raw material is all join to be re-fed into banbury in blender after stirring under normal conditions, but the PUR of the present invention selects to add when banburying, and the performance of product can be made to reach the best。Adding PUR in blender can make PUR cross-link in advance in stirring generating section, makes properties of product not good。If just adding PUR when opening refining in selection, the mixing that can make PUR is uniform not, and the product uniformity is poor。
By by after mixing for foaming layer raw material and adopt rolling-molding method or extrusion moulding to produce to roll and foaming layer, the foaming layer of calendering or extrusion is fitted with bottom fabricbase while hot；Again by after mixing for foaming layer raw material and adopt rolling-molding method to produce to roll and foaming layer, the surface layer of calendering or extrusion obtains TPU membrane or sheet material with foaming layer laminating while hot。Again TPU membrane or sheet material are placed 0.5～5 day, carry out moisture-curable。Finally the TPU membrane after moisture-curable or sheet material are heated and foam, obtain finished product。By directly bonding in the course of processing, need not adopting adhesive, the adhesive property between its each layer is superior。Moisture cured polyurethane hot melt joins the cross-linking agent effect in foaming layer raw material as foaming layer, place a couple of days after calendering or extrusion molding, before foaming, TPU membrane or sheet material are carried out moisture-curable, make the internal material generating section crosslinking curing of TPU membrane or sheet material, TPU melt strength can be improved, can avoid producing excessive and uneven abscess when foaming, improve the uniformity of foam bubble and the toughness of material。
Detailed description of the invention
Technical scheme is described further by construction embodiment below。
The invention provides the TPU expanded material of a kind of single layer structure, the following component including with parts by weight: thermoplastic polyurethane 100 parts, foaming agent 1～10 part and PUR 3～30 parts。
The shore hardness of above-mentioned thermoplastic polyurethane is 45A～50D, and PUR adopts moisture cured polyurethane hot melt。
The preparation method of above-mentioned TPU expanded material, comprises the steps:
1) by after mixing for raw material and adopt rolling-molding method or extrusion moulding to produce TPU membrane or sheet material；
2) by step 1) TPU membrane produced or sheet material temperature be 15～55 DEG C, humidity condition more than 65% transfer and set to 0 .5～5 day, carry out moisture-curable。
3) TPU membrane after moisture-curable or sheet material are sent into foaming furnace heat to 170～230 DEG C and foam, obtain finished product。
Can adopting point four sections of control temperature in foaming furnace, one section of temperature of feed end is 180 ± 10 DEG C, to material preheater, the temperature of second segment is 200 ± 10 DEG C, 3rd section of temperature is 220 ± 10 DEG C, and TPU membrane or sheet material foam gradually in these two sections, and a section of discharge end is 190 ± 10 DEG C。Foamed time is 1～2 minute。
Step 1) calendering formation temperature at 115～150 DEG C。
Step 1) in the manufacturing process of rolling-molding method as follows:
A, other foaming layer raw material beyond heat extraction melten gel is put in blender stirring mixing；
B, mixed for stirring raw material is sent in the lump together with PUR banbury carries out banburying；
C, raw material banburying completed are sent in mill and are carried out out refining；
D, open refining after raw material be re-fed in calender to carry out calendering formation after filtering。
The following example 1～3 is the specific embodiment of the TPU expanded material making above-mentioned single layer structure:
Embodiment 1
The present embodiment is by changing the time of moisture-curable, temperature and humidity with raw a series of Related products, and the performance parameters such as the expansion ratio of Related product, cell uniformity, hot strength, tearing strength are detected, to test the time of moisture-curable, the temperature and humidity impact on properties of product。
Raw material includes the following component with parts by weight: the thermoplastic polyurethane that shore hardness is 45A 100 parts, foaming agent 4,4-OBSH 10 parts, PUR 15 parts；
Step 1) adopt rolling-molding method to prepare foaming layer, rolling temperature is 115 DEG C；
Step 2) in the temperature of moisture-curable take 15 DEG C, 35 DEG C and 55 DEG C, humidity takes 65%, 80% and 95%, and the time takes 0.5 day, 3 days and 5 is series contrast experiment respectively。
The expansion ratio of product made, cell uniformity, hot strength, tearing strength are detected。Concrete value parameter and result are as follows:
By above-mentioned experimental data it can be seen that high humility, under high-temperature, needed for properties of product reach more satisfactory state, the moisture-curable time is short；Under low humidity, low temperature, needed for properties of product reach more satisfactory state, the moisture-curable time is long。
Embodiment 2
The present embodiment adopts when other condition is constant, only change the contrast experiment of foaming agent consumption, and the performance parameters such as the expansion ratio of experimental products, cell uniformity, hot strength, tearing strength are detected, to test the foaming agent consumption impact on properties of product。
Raw material includes the following component with parts by weight: the thermoplastic polyurethane that shore hardness is 80A 100 parts, foaming agent adopt azodicarbonamide to take 1 part, 3 parts, 5 parts, 7 parts and 10 parts, PUR 30 parts respectively；
Step 1) in adopt extrusion moulding prepare foaming layer；
Step 2) in the temperature of moisture-curable be 30 DEG C, humidity is 85%, and the time is 3 days。
The expansion ratio of product made, cell uniformity, hot strength, tearing strength are detected。Concrete value parameter and result are as follows:
By above-mentioned experimental data it can be seen that foaming agent consumption is notable on expansion ratio impact, foaming agent consumption is more big, and expansion ratio is more big。
Embodiment 3
The present embodiment adopts when other condition is constant, only changes the contrast experiment of PUR consumption, and provides the contrast experiment replacing PUR with crosslink agent DCP。The performance parameters such as the expansion ratio of experimental products, cell uniformity, hot strength, tearing strength are detected, with the impact on properties of product of the PUR consumption。
Raw material includes the following component with parts by weight: the thermoplastic polyurethane that shore hardness is 50D 100 parts, foaming agent azodicarbonamide 5 parts, PUR 3 parts, 10 parts, 20 parts and 30 parts；
Step 1) in adopt rolling-molding method prepare foaming layer, rolling temperature is 150 DEG C；
Step 2) in the temperature of moisture-curable be 25 DEG C, humidity is 95%, and the time is 4 days。
The expansion ratio of product made, cell uniformity, hot strength, tearing strength are detected。Concrete value parameter and result are as follows:
Present invention also offers the TPU expanded material of a kind of three-decker, including the surface layer being sequentially connected with, foaming layer and bottom fabricbase。
The raw material making surface layer includes the following component with parts by weight: thermoplastic polyurethane 100 parts, 0.1～2 part of antioxidant, ultraviolet (UV) resistant agent 0.1～4 part and fire retardant 1～20 part；
The raw material making surface layer preferably comprises the following component with parts by weight: thermoplastic polyurethane 100 parts, 0.5～1 part of antioxidant, ultraviolet (UV) resistant agent 0.5～2 part and fire retardant 5～13 parts。
The raw material making foaming layer includes the following component with parts by weight: thermoplastic polyurethane 100 parts, foaming agent 1～10 part, PUR 3～30 parts, 0.1～2 part of antioxidant and fire retardant 5～50 parts；
The raw material making foaming layer preferably comprises the following component with parts by weight: thermoplastic polyurethane 100 parts, 0.3～2 part of antioxidant, ultraviolet (UV) resistant agent 0.3～4 part and fire retardant 1～20 part。
The raw material of above-mentioned surface layer and the raw material of foaming layer all can add appropriate pigment。
Thermoplastic polyurethane adopts shore hardness to be the Polyurethane Thermoplastic Elastomer of 45A～50D, it is preferable that hardness is 45A～95A。Bottom fabricbase can adopt looped fabric, comb to weave cotton cloth or non-woven fabrics。PUR adopts moisture cured polyurethane hot melt。
Antioxidant adopts one or more mixing in antioxidant 1010, antioxidant 1076, antioxidant 245, irgasfos 168 and antioxidant DDPP。
Ultraviolet (UV) resistant agent adopts one or more mixing in benzotriazole, benzophenone, triazine。
Fire retardant adopts halogen-free flame retardants。
Foaming agent adopts one or more in azodicarbonamide, 4,4-OBSH, p-toluene sulfonylsemicarbazide and sodium bicarbonate。
Present invention also offers the Preparation Method of above-mentioned TPU expanded material, comprise the steps:
1) the foaming layer raw material beyond heat extraction melten gel being sent into blender to stir 20～30 seconds, more mixed for stirring raw material is sent to together with PUR banbury in the lump carries out banburying, banburying temperature is 100～115 DEG C, and the banburying time is 40～60 seconds。Raw material banburying completed is sent in mill and is carried out out refining at 100～110 DEG C；Open the raw material after refining and obtain foaming layer through calender calendering formation when temperature is 115～150 DEG C, roll the foaming layer and be sent to make-up machine in the lump together with bottom fabricbase and fit while hot；
2) be re-fed into banbury and carry out banburying after surface layer raw material being sent into blender stirring, after be re-fed in mill to carry out out refining；Open the raw material after refining and obtain surface layer through calender calendering formation when temperature is 115～150 DEG C, roll the surface layer that and be sent to make-up machine while hot with the above-mentioned foaming layer posted and bottom fabricbase in the lump and fit while hot and obtain TPU membrane or sheet material, rolling；
3) by step 2) TPU membrane that obtains or sheet material temperature be 15～55 DEG C, humidity condition more than 65% transfer and set to 0 .5～5 day, carry out moisture-curable。
4) TPU membrane after moisture-curable or sheet material are sent into foaming furnace, be at 170～230 DEG C, be heated foaming in temperature, obtain finished product。
Can adopting point four sections of control temperature in foaming furnace, one section of temperature of feed end is 180 ± 10 DEG C, to material preheater, the temperature of second segment is 200 ± 10 DEG C, 3rd section of temperature is 220 ± 10 DEG C, and TPU membrane or sheet material foam gradually in these two sections, and a section of discharge end is 190 ± 10 DEG C。Foamed time is 1～2 minute。
The following example 5～11 is the specific embodiment of the TPU expanded material making above-mentioned three-decker:
Embodiment 4
Surface layer raw material includes the following component with parts by weight: the thermoplastic polyurethane that shore hardness is 45A 100 parts, antioxidant 1010 (four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester) 1 part, ultraviolet (UV) resistant agent benzotriazole 0.1 part, fire retardant 5 parts, pigment 0.01 part；
Foaming layer raw material includes the following component with parts by weight: the thermoplastic polyurethane that shore hardness is 80A 100 parts, foaming agent 4,4-OBSH 10 parts, PUR 3 parts, antioxidant 1010 (four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester) 0.1 part, fire retardant 5 parts, pigment 0.01 part；
Step 1) in preparation foaming layer rolling temperature be 115 DEG C；
Step 2) in prepare the rolling temperature of surface layer be 150 DEG C；
Step 3) in the temperature of moisture-curable be 15 DEG C, humidity is 85%, and the time is 3 days。
Embodiment 5
Surface layer raw material includes the following component with parts by weight: the thermoplastic polyurethane that shore hardness is 50D 100 parts, antioxidant 1076 (β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid octadecanol ester) 2 parts, ultraviolet (UV) resistant agent 3 parts, fire retardant 20 parts, pigment 0.01 part；
Foaming layer raw material includes the following component with parts by weight: the thermoplastic polyurethane that shore hardness is 95A 100 parts, foaming agent 6 parts, PUR 30 parts, 0.5 part of antioxidant, fire retardant 10 parts, pigment 0.01 part；
Step 1) in preparation foaming layer rolling temperature be 150 DEG C；
Step 2) in prepare the rolling temperature of surface layer be 150 DEG C；
Step 3) in the temperature of moisture-curable be 10 DEG C, humidity is 95%, and the time is 4 days。
Embodiment 6
Surface layer raw material includes the following component with parts by weight: the thermoplastic polyurethane that shore hardness is 75A 100 parts, 0.5 part of antioxidant 245 (triethylene glycol ether-two (3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester), ultraviolet (UV) resistant agent 0.5 part, fire retardant 13 parts, pigment 0.01 part；
Foaming layer raw material includes the following component with parts by weight: the thermoplastic polyurethane that shore hardness is 75A 100 parts, foaming agent 1 part, PUR 10 parts, 1 part of antioxidant, fire retardant 13 parts, pigment 0.01 part；
Step 1) in preparation foaming layer rolling temperature be 115 DEG C；
Step 2) in prepare the rolling temperature of surface layer be 125 DEG C；
Step 3) in the temperature of moisture-curable be 55 DEG C, humidity is 75%, and the time is 1 day。
Embodiment 7
Surface layer raw material includes the following component with parts by weight: the thermoplastic polyurethane that shore hardness is 40D 100 parts, irgasfos 168 (three [2.4-di-tert-butyl-phenyl] phosphite ester) 0.1 part, ultraviolet (UV) resistant agent 4 parts, fire retardant 1 part, pigment 0.01 part；
Foaming layer raw material includes the following component with parts by weight: the thermoplastic polyurethane that shore hardness is 70A 100 parts, foaming agent 6 parts, PUR 20 parts, 2 parts of antioxidant, fire retardant 30 parts, pigment 0.01 part；
Step 1) in preparation foaming layer rolling temperature be 115 DEG C；
Step 2) in prepare the rolling temperature of surface layer be 115 DEG C；
Step 3) in the temperature of moisture-curable be 25 DEG C, humidity is 65%, and the time is 0.5 day。
Embodiment 8
Surface layer raw material includes the following component with parts by weight: the thermoplastic polyurethane that shore hardness is 45A 100 parts, antioxidant DDPP (diphenylisodecyl base ester) 1 part, ultraviolet (UV) resistant agent 2 parts, fire retardant 5 parts, pigment 0.01 part；
Foaming layer raw material includes the following component with parts by weight: the thermoplastic polyurethane that shore hardness is 75A 100 parts, foaming agent 5 parts, PUR 15 parts, 0.8 part of antioxidant, fire retardant 50 parts, pigment 0.01 part；
Step 1) in preparation foaming layer rolling temperature be 125 DEG C；
Step 2) in prepare the rolling temperature of surface layer be 115 DEG C；
Step 3) in the temperature of moisture-curable be 30 DEG C, humidity is 80%, and the time is 5 days。
Embodiment 9
Surface layer raw material includes the following component with parts by weight: the thermoplastic polyurethane that shore hardness is 90A 100 parts, antioxidant 1010 (four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester) 1 part, antioxidant 1076 (β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid octadecanol ester) 1 part, ultraviolet (UV) resistant agent 1 part, fire retardant 8 parts, pigment 0.01 part；
Foaming layer raw material includes the following component with parts by weight: the thermoplastic polyurethane that shore hardness is 85A 100 parts, foaming agent 8 parts, PUR 20 parts, irgasfos 168 (three [2.4-di-tert-butyl-phenyl] phosphite ester) 1.5 parts, fire retardant 40 parts, pigment 0.01 part；
Step 1) in preparation foaming layer rolling temperature be 150 DEG C；
Step 2) in prepare the rolling temperature of surface layer be 150 DEG C；
Step 3) in the temperature of moisture-curable be 20 DEG C, humidity is 70%, and the time is 2 days。
Embodiment 10
Surface layer raw material includes the following component with parts by weight: the thermoplastic polyurethane that shore hardness is 80A 100 parts, fire retardant 8 parts；
Foaming layer raw material includes the following component with parts by weight: the thermoplastic polyurethane that shore hardness is 80A 100 parts, foaming agent 8 parts, PUR 20 parts, fire retardant 10 parts；
Step 1) in preparation foaming layer rolling temperature be 115 DEG C；
Step 2) in prepare the rolling temperature of surface layer be 150 DEG C；
Step 3) in the temperature of moisture-curable be 20 DEG C, humidity is 80%, and the time is 3 days。
The expansion ratio of product of above-described embodiment making, cell uniformity, hot strength, tearing strength are detected。Testing result is following table such as:
Can be seen that from above-mentioned detection data, the product of the present invention there is good toughness, scratch resistance performance, resistance to tortuosity, may replace the PVC of the prior art surface decoration material as furniture or automotive trim。And there is good color fastness, hydrolytic resistance and anti-flammability, attractive in appearance, be unlikely to deform, product specification is high, long service life。
Above-described is only some embodiments of the present invention。For the person of ordinary skill of the art, without departing from the concept of the premise of the invention, it is also possible to make some deformation and improvement, these broadly fall into the protection domain of invention。

Claims (6)

1.TPU expanded material, the following component including with parts by weight: thermoplastic polyurethane 100 parts, foaming agent 1～10 part and PUR 3～30 parts。
The shore hardness of above-mentioned thermoplastic polyurethane is 45A～50D, and PUR adopts moisture cured polyurethane hot melt。
2.TPU expanded material, including the surface layer being sequentially connected with, foaming layer and bottom fabricbase, wherein,
The raw material making surface layer includes the following component with parts by weight: thermoplastic polyurethane 100 parts；
The raw material making foaming layer includes the following component with parts by weight: thermoplastic polyurethane 100 parts, foaming agent 1～10 part and PUR 3～30 parts；
The shore hardness of above-mentioned thermoplastic polyurethane is 45A～50D, and PUR adopts moisture cured polyurethane hot melt。
3. the preparation method of TPU expanded material according to claim 1, comprises the steps:
1) by after mixing for raw material and adopt rolling-molding method or extrusion moulding to produce TPU membrane or sheet material；
2) by step 1) TPU membrane that produces or sheet material be that 15～55 DEG C of humidity condition more than 65% is transferred and set to 0 .5～5 day in temperature, carries out moisture-curable。
3) TPU membrane after moisture-curable or sheet material are heated foam, obtain finished product。
4. its preparation method of TPU expanded material according to claim 3, it is characterised in that step 1) calendering formation temperature at 115～150 DEG C。
5. its preparation method of TPU expanded material according to claim 3, it is characterised in that step 3) blowing temperature be 170～230 DEG C。
6. its preparation method of TPU expanded material according to claim 3, it is characterised in that step 1) in the manufacturing process of rolling-molding method as follows:
A, other foaming layer raw material beyond heat extraction melten gel is put in blender stirring mixing；
B, mixed for stirring raw material is sent in the lump together with PUR banbury carries out banburying；
C, raw material banburying completed are sent in mill and are carried out out refining；
D, open refining after raw material be re-fed in calender to carry out calendering formation after filtering。
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WO2018010271A1 (en) * 2016-07-11 2018-01-18 浙江新恒泰新材料有限公司 High expansion thermoplastic polyurethane microporous foam sheet and production method therefor
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CN113563629A (en) * 2021-07-27 2021-10-29 东莞市米儿塑胶原料有限公司 Preparation method of electromagnetic wave shielding TPU
CN113878904A (en) * 2021-09-26 2022-01-04 福慕斯(山东)新材料有限公司 Production method of prefabricated E-TPU (expanded thermoplastic polyurethane) plate
CN114181516A (en) * 2021-12-13 2022-03-15 福建恩迈特新材料有限公司 TPU foaming composition, foaming material and preparation method thereof

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