WO2022252700A1 - 一种热塑性弹性体物理发泡卷材及其半连续制备方法 - Google Patents

一种热塑性弹性体物理发泡卷材及其半连续制备方法 Download PDF

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WO2022252700A1
WO2022252700A1 PCT/CN2022/077102 CN2022077102W WO2022252700A1 WO 2022252700 A1 WO2022252700 A1 WO 2022252700A1 CN 2022077102 W CN2022077102 W CN 2022077102W WO 2022252700 A1 WO2022252700 A1 WO 2022252700A1
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thermoplastic elastomer
coil
physical foaming
pressure fluid
impregnated
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PCT/CN2022/077102
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English (en)
French (fr)
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翟文涛
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中山大学
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Publication of WO2022252700A1 publication Critical patent/WO2022252700A1/zh
Priority to US18/204,387 priority Critical patent/US20230323065A1/en

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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
    • C08J9/04—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
    • 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
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3415—Heating or cooling
    • 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
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • C08J9/0066—Use of inorganic compounding ingredients
    • 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
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/04—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould using liquids, gas or steam
    • B29C35/045—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould using liquids, gas or steam using gas or flames
    • B29C2035/046—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould using liquids, gas or steam using gas or flames dried air
    • 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
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/04—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould using liquids, gas or steam
    • B29C35/041—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould using liquids, gas or steam using liquids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2021/00—Use of unspecified rubbers as moulding material
    • B29K2021/003—Thermoplastic elastomers
    • 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/03—Extrusion of the foamable blend
    • 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
    • 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
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/22—Thermoplastic resins
    • 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
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/26—Elastomers
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • 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
    • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids

Definitions

  • the invention relates to the field of thermoplastic elastomer foamed leather, in particular to a thermoplastic elastomer physically foamed roll material and a semi-continuous preparation method thereof.
  • General polymer foam leather (such as PVC leather, PU leather, etc.) involves the use and emission of a large amount of chlorides, sulfides, solvents, and plasticizers during the processing process, and there is a problem of VOC release in products. Applications in leather and other fields are limited.
  • thermoplastic polyurethane (TPU), polyester elastomer (TPEE), and nylon elastomer (TPAE) are more environmentally friendly materials than traditional polymers, and they have excellent wear resistance and scratch resistance. Poor performance, mechanical strength, air permeability, water and oil resistance, bacteria resistance, and the ability to melt and recycle.
  • TPU foam film prepared by TPU resin is a kind of artificial leather material with wide application prospects.
  • CN111484725A, CN108285634A all disclose TPU foamed leather and preparation technology thereof, have used AC foaming agent, microsphere foaming agent or the compound of above-mentioned foaming agent as additive in the preparation scheme of these products, by the technology of extrusion calendering To prepare TPU foam film.
  • AC foaming agent and microsphere foaming agent have the problem of incomplete decomposition during processing, which easily leads to environmental protection problems; at the same time, the use of chemical foaming agents to prepare TPU foam leather also has large foam cell sizes, The problem of low foam expansion ratio.
  • CN105714574B discloses a method for preparing foamed TPU artificial leather by continuous extrusion of supercritical fluid.
  • TPU resin is continuously melted in the first extruder, and supercritical fluid such as CO is injected at the end of the first extruder .
  • supercritical fluid such as CO
  • the polymer/fluid mixture is injected into the second extruder through the melt pump, and the TPU foam film is prepared through the second extruder by touch casting.
  • the high-pressure fluid diffuses too fast in the high-temperature extrusion die, and the high-pressure fluid is easy to escape from the polymer melt.
  • the escape degree of the high-pressure fluid is significantly increased, so it is difficult to prepare a TPU foam film with a thickness of less than 1 mm and a uniform cell size distribution by this method; at the same time, the rapid escape of the high-pressure fluid also leads to There are surface defects such as air marks and wavy lines on the surface of the bubble film.
  • CN104611942B discloses a method for preparing foam leather by continuous extrusion and foaming of supercritical N2 fluid. Although this method can produce low-thickness products, the solubility of N 2 in TPU is low during the preparation process, and the density of the prepared TPU foam leather is generally 0.4-0.8 g/cm 3 , which has the problem of high density. At the same time, in the process of continuous extrusion and foaming, there is still the problem that high-pressure fluid is easy to escape at high temperature, resulting in defects such as air marks and wavy lines on the skin of foamed film products.
  • CN103951965B discloses a method for preparing a TPU foam sheet.
  • a colored TPU sheet is impregnated with a high-pressure fluid, and then the colored TPU sheet is heated and foamed in a water bath to finally obtain a colored TPU foam sheet.
  • the high-pressure fluid will still diffuse and escape from the impregnated TPU sheet at normal temperature and pressure, causing the high-pressure fluid-impregnated TPU sheet to fail to foam after being placed at normal temperature and pressure for a period of time.
  • CN108479431B discloses a method of combining two layers of gas barrier film and TPU film into a sandwich structure. Since the gas barrier film can prevent high-pressure fluid from escaping from the impregnated TPU film, it can be prepared with a thickness lower than 0.1mm. TPU film.
  • the interfacial adhesion strength between the barrier film and the TPU film will affect the foaming behavior of TPU, resulting in different expansion behavior and cell morphology. Therefore, the technology of using gas barrier film to improve the foaming of TPU film is in There are challenges in large-scale implementation. At the same time, the price of the barrier film is high, and the use of such raw materials will also lead to higher product processing costs.
  • the TPU film impregnated with high-pressure fluid foaming agent is prone to desorption when placed at room temperature and pressure for a long time, and the escape of a large amount of foaming agent leads to instability in the TPU foaming process, which also limits the large-scale production of TPU foamed film coils. preparation.
  • the object of the present invention is to provide a semi-continuous preparation method of a thermoplastic elastomer physical foaming coil, in which the thermoplastic elastomer coil is subjected to rapid freezing and air-locking treatment after high-pressure fluid impregnation, Not only does the impregnated coil not lose weight significantly during the foaming process, but the escape rate of the high-pressure fluid in the coil is significantly reduced, and at the same time it can realize long-distance transportation of the coil and continuous heating and foaming; this method can realize large-scale Continuous production, safety and environmental protection, the obtained product has smooth surface, thinner thickness, low density and small and uniform foaming cells.
  • thermoplastic elastomer physical foaming coil comprises the following steps:
  • thermoplastic elastomer coil After drying, pre-mixing, twin-screw continuous extrusion, calendering and winding of the thermoplastic elastomer and the auxiliary agent in sequence, the precursor thermoplastic elastomer coil is obtained;
  • thermoplastic elastomer coil obtained in step (1) immerse the precursor thermoplastic elastomer coil obtained in step (1) into a high-pressure fluid to obtain an impregnated thermoplastic elastomer coil, and then subject the impregnated thermoplastic elastomer coil to rapid freezing and air-locking treatment and store at low temperature; the impregnated The mass content of high-pressure fluid in the thermoplastic elastomer coil is 1 to 15%; the temperature of the quick freezing and air lock treatment is -20 to -100°C; the temperature of the low temperature storage is -60 to -20°C;
  • thermoplastic elastomer coil material stored at low temperature into the heating medium and heat it for physical foaming, after rolling, cooling, and winding, the thermoplastic elastomer physical foam coil material is obtained;
  • the heating medium is hot air or hot water.
  • thermoplastic elastomer coil After the high-pressure fluid impregnated thermoplastic elastomer coil is subjected to rapid freezing and air-locking treatment, the molecular chain movement of the elastomeric polyester is frozen, and then the movement of the high-pressure fluid molecule is also imprisoned to the maximum extent, so that the impregnated thermoplastic elastomer
  • the coil can be stored or transported at a specific low temperature for a long time, and the desorption rate of high-pressure fluid molecules is significantly reduced during storage and subsequent foaming, which is conducive to maintaining the weight loss rate of the thermoplastic elastomer coil.
  • the inventor found that when the impregnated thermoplastic elastomer coil is subjected to freezing and air-locking treatment at -20 to -100°C, its effect and implementation feasibility are the highest: when the temperature is lower than -100°C The molecular confinement rate of high-pressure fluid is not high, and at the same time, the requirements for equipment are increased, and the cost is significantly increased. When the temperature is higher than -20°C, the probability of molecular movement of high-pressure fluid increases, and the optimal weight loss rate cannot be guaranteed.
  • thermoplastic elastomer physical foaming coil described in the present invention, by controlling the solubility content of the high-pressure fluid in the thermoplastic elastomer coil, and then performing rapid freezing and air-locking treatment on the material at a specific temperature, the high-pressure fluid is suppressed.
  • the obtained impregnated coils can be stored at low temperature for a long time or carried out long-distance transportation, and at the same time can be stably continuously heated and foamed, and no obvious damage will occur in the storage or foaming process as in the prior art
  • the high-pressure fluid escapes, and the operability is significantly improved; the method can realize large-scale continuous production, is safe and environmentally friendly, and the prepared product has a smooth surface, a thinner thickness, a low density, and the foaming cells are small and uniform.
  • the Shore hardness of the thermoplastic elastomer in step (1) is 60-95A, and the thickness of the precursor thermoplastic elastomer coil is 0.1-3 mm.
  • the impregnation and foaming effects of the subsequent high-pressure fluid and the performance of the final product can be guaranteed, and the impregnation rate of the high-pressure fluid is too high or too low due to unsatisfactory thickness, and the foaming effect is not good; or The mechanical properties of the product are poor due to insufficient hardness.
  • thermoplastic elastomer in step (1) includes at least one of TPU, TPEE, and TPAE, and the auxiliary agent includes a nucleating agent and an antioxidant;
  • the addition of the thermoplastic elastomer in step (1) is 100 parts by weight, the addition of the nucleating agent is 0 to 20 parts by weight, and the addition of the antioxidant is 0 parts by weight ⁇ 1 serving.
  • thermoplastic elastomer When a specific content of antioxidant and nucleating agent is added, the stability of the obtained thermoplastic elastomer is higher, and at the same time, the crystallinity of the thermoplastic elastomer coil after impregnated with high-pressure fluid can be optimized, and the impregnated coil can be further suppressed during storage and development. The weight loss phenomenon during the soaking process.
  • the parts by weight of the TPU are 1-99 parts; more preferably, the parts by weight of the TPU are 5-30 parts or 70-95 parts .
  • the glass transition temperature of TPU, TPEE, and TPAE is about -30 ⁇ -50°C, and the hardness and other properties of the three are relatively close.
  • the addition ratio of the three can be adjusted according to the actual production. Bubble flat thermoplastic elastomer sheet.
  • the nucleating agent includes an organic nucleating agent and an inorganic nucleating agent
  • the organic nucleating agent includes at least one of EVA, POE, OBC, SBES, EPDM
  • the inorganic nucleating agent includes calcium carbonate , talcum powder, mica, glass microspheres at least one.
  • the auxiliary agent in step (1) further includes 1-20 parts of gas barrier agent.
  • thermoplastic elastomers Compared with general polymer polyesters, the frequency of molecular diffusion motion in thermoplastic elastomers is higher, and compared with general foaming materials, it is more prone to gas escape during the foaming process, resulting in a significant decrease in foaming efficiency.
  • a dense cross-linked network can be formed in the thermoplastic elastomer coil by adding an appropriate gas barrier agent, which can effectively imprison the impregnated high-pressure fluid and reduce the desorption rate of the high-pressure fluid.
  • the gas barrier includes at least one of PVOH and PVA;
  • the gas barrier agent is PVOH.
  • the precursor thermoplastic elastomer coiled material in step (1) also contains a gas barrier layer
  • the preparation method of the precursor thermoplastic elastomer coiled material is: the thermoplastic elastomer and the auxiliary agent are sequentially dried, pre-mixed, twin-screw After continuous extrusion and calendering, the surface of the elastomer is coated with an aqueous solution containing PVA, and then dried and rolled to obtain a precursor thermoplastic elastomer coil.
  • the PVA aqueous solution is used for coating modification during the preparation process of the current flooding thermoplastic elastomer coil.
  • the formed PVA film can also inhibit the high-pressure fluid from escaping during storage and foaming. and because the preparation method of the present invention includes quick freezing and air-locking treatment, compared with the prior art, this PVA film can guarantee the low desorption of high-pressure fluid, and simultaneously the film has high compatibility with thermoplastic elastomers, and will not This results in obvious expansion and cell shape differences; the modified coating and drying steps are simple and easy to implement, and will not increase the processing cost.
  • the thickness of the gas barrier layer is 0.01-0.05 mm.
  • the mass content of PVA in the aqueous solution of PVA is 5-30%;
  • the mass content of PVA in the aqueous solution of PVA is 10-20%.
  • the high-pressure fluid in step (2) includes at least one of CO 2 fluid and N 2 fluid.
  • the pressure of the high-pressure fluid during the impregnation in step (2) is 1-7 MPa, and the impregnation time is 1-24 hours.
  • the mass content of the high-pressure fluid in the impregnated thermoplastic elastomer coil obtained after impregnating in step (2) is 2-10%.
  • the quick freezing and gas-locking treatment in step (2) is carried out with liquid nitrogen or dry ice.
  • the temperature of the rapid freezing and air-locking treatment in step (2) is -50 to -80°C.
  • thermoplastic elastomers have already undergone vitrification at -30 to -50°C, when the temperature is maintained within the above-mentioned preferred range, it is sufficient to limit the movement and escape of high-pressure fluid. And can increase production cost and difficulty.
  • the mass loss of the impregnated thermoplastic elastomer coil material stored at low temperature in step (3) is 0-50%/day;
  • the mass loss of the impregnated thermoplastic elastomer coils stored at low temperature is 5-30%/day;
  • the mass loss of the impregnated thermoplastic elastomer coils stored at low temperature is 5-20%/day;
  • the mass loss of the impregnated thermoplastic elastomer coil stored at low temperature is 5-10%/day.
  • the high-pressure fluid is confined in the thermoplastic elastomer coil, and the weight loss rate is significantly reduced.
  • the weight loss rate of the impregnated thermoplastic elastomer coil can reach a minimum of 5- 10%/day.
  • the mass weight loss rate (%) of the impregnated thermoplastic elastomer coil stored at low temperature (m 1 -m 2 ) ⁇ 100%/(m 1 -m 0 );
  • m 0 is the mass of the precursor thermoplastic elastomer coil
  • m 1 is the mass of the impregnated thermoplastic elastomer coil after high-pressure fluid impregnation and normal temperature and pressure desorption for 10 minutes
  • m 2 is the mass of the impregnated thermoplastic elastomer coil after freezing After air-locking and low-temperature storage, the mass of the impregnated thermoplastic elastomer coil after desorption at room temperature and pressure for 10 minutes.
  • Another object of the present invention is to provide the thermoplastic elastomer physical foaming coil prepared by the semi-continuous preparation method of the thermoplastic elastomer physical foaming coil, and the thermoplastic elastomer physical foaming coil passes through Rapid freezing and air-locking and low-temperature storage treatment, the thickness of the thermoplastic elastomer physical foaming coil is 0.1-3mm, the density is 0.1-0.6g/cm 3 , the size of the foaming cells is 1-200 ⁇ m, and the Shore hardness It is 20 ⁇ 60C.
  • the polyester foam coil product provided by the present invention has a thinner thickness (less than 0.1 mm) and a lower density due to the special treatment that suppresses the escape of high-pressure fluid.
  • the foaming process of the product is smooth and uniform, and the surface after foaming is smooth and smooth, with high quality and excellent mechanical properties.
  • thermoplastic elastomer physically foamed coil has a thickness of 0.5-2mm.
  • thermoplastic elastomer physically foamed coil includes a non-foamed skin layer and a foamed core layer inside, and the size of the foamed cells in the foamed core layer is 10-50 ⁇ m.
  • the length of the thermoplastic elastomer physically foamed coil is ⁇ 50m.
  • the resulting product can retain a complete and ideal length, which is suitable for various application fields.
  • the beneficial effect of the present invention is that the present invention provides a semi-continuous preparation method of the thermoplastic elastomer physical foaming coil, by controlling the solubility content of the high-pressure fluid in the thermoplastic elastomer coil, and then at a specific temperature
  • the material is subjected to rapid freezing and air-locking treatment to inhibit the desorption of high-pressure fluid.
  • the obtained impregnated coil can be stored at low temperature for a long time or transported remotely. At the same time, it can be continuously heated and foamed stably. During the process, there will be no obvious high-pressure fluid escape like the prior art, and the implementability is significantly improved; the method can realize large-scale continuous production, and is safe and environmentally friendly.
  • the present invention also provides the thermoplastic elastomer physical foaming roll material prepared by the preparation method.
  • the thickness of the product is 0.1-3 mm, the density is 0.1-0.6 g/cm 3 , and the size of the foaming cells is 1-200 ⁇ m. Its hardness is 20 ⁇ 60C.
  • Fig. 1 is the optical photograph of thermoplastic elastomer physical foaming roll material of the present invention
  • Fig. 2 is a cross-sectional scanning electron microscope image of the thermoplastic elastomer physically foamed roll material of the present invention.
  • the high-pressure fluid content (%) (m 2 -m 0 ) ⁇ 100%/m 0 in the impregnated polyester coils that have undergone rapid freezing and air-locking treatment and low-temperature storage in each embodiment and comparative example;
  • m 0 is the mass of the precursor thermoplastic elastomer coil
  • m 2 is the mass of the impregnated thermoplastic elastomer coil after desorption at room temperature and pressure for 10 minutes after the impregnated thermoplastic elastomer coil has been subjected to rapid freezing and air-locking treatment and low-temperature storage .
  • thermoplastic elastomer physical foaming coil of the present invention comprises the following steps:
  • thermoplastic elastomer coil material obtained in step (1) into a high-pressure container filled with CO2 fluid and impregnate to obtain a high-pressure fluid content of 9% impregnated thermoplastic elastomer coil material, and then move the impregnated thermoplastic elastomer coil material into
  • the cooling chamber adopts liquid nitrogen for rapid freezing and air-locking treatment. At this time, the temperature in the cooling chamber is -60°C, and then stored at -20°C for 1 hour at low temperature. After 1 hour of low temperature storage, impregnate the high-pressure fluid in the thermoplastic elastomer physical foaming coil The content is 8.2%, and the mass weight loss rate of high-pressure fluid is 8.9%;
  • thermoplastic elastomer physical foaming roll material stored at low temperature into the heating medium and heat it for physical foaming, after rolling, cooling, and winding, the thermoplastic elastomer physical foaming roll is obtained material.
  • thermoplastic elastomer physical foaming coil After testing, as shown in Figure 1, the obtained thermoplastic elastomer physical foaming coil has a smooth surface, a thickness of 0.5 mm, a length of 60 m, a density of 0.2 g/cm 3 , and uniform foam cells, as shown in Figure 2 According to the results, the average size of the foamed cells in the core layer is about 25.8 ⁇ m, and the Shore hardness is 30C.
  • thermoplastic elastomer physical foaming coil of the present invention comprises the following steps:
  • thermoplastic elastomer coil material obtained in step (1) into a high-pressure container filled with CO2 fluid and impregnate to obtain a high-pressure fluid content of 9% impregnated thermoplastic elastomer coil material, and then move the impregnated thermoplastic elastomer coil material into
  • the cooling chamber adopts liquid nitrogen for rapid freezing and air lock treatment. At this time, the temperature in the cooling chamber is -60°C, and then stored at -20°C for 6 hours at low temperature. After 6 hours of low temperature storage, impregnate the high-pressure fluid in the thermoplastic elastomer physical foaming coil The content is 7.8%, and the mass weight loss rate of high-pressure fluid is 13.3%;
  • thermoplastic elastomer physical foaming roll material stored at low temperature into the heating medium and heat it for physical foaming, after rolling, cooling, and winding, the thermoplastic elastomer physical foaming roll is obtained material.
  • thermoplastic elastomer physical foaming coil has a smooth surface, a thickness of 1.5mm, a length of 58m, a density of 0.3g/cm 3 , and uniform foam cells.
  • the average size of the foam cells in the core layer is about 30.4 ⁇ m, Shore hardness is 38C.
  • thermoplastic elastomer physical foaming coil of the present invention comprises the following steps:
  • thermoplastic elastomer roll with a thickness of 0.5mm is obtained material
  • thermoplastic elastomer coil material obtained in step (1) into a high-pressure container filled with CO2 fluid to obtain an impregnated thermoplastic elastomer coil material with a high-pressure fluid content of 8.5%, and then move the impregnated thermoplastic elastomer coil material into
  • the cooling chamber adopts liquid nitrogen for rapid freezing and air lock treatment. At this time, the temperature in the cooling chamber is -60°C, and then stored at -20°C for 24 hours at low temperature. After 24 hours of low temperature storage, impregnate the high-pressure fluid in the thermoplastic elastomer physical foaming coil The content is 6.5%, and the mass weight loss rate of high-pressure fluid is 23.5%;
  • thermoplastic elastomer physical foaming roll material stored at low temperature into the heating medium and heat it for physical foaming, after rolling, cooling, and winding, the thermoplastic elastomer physical foaming roll is obtained material.
  • thermoplastic elastomer physical foaming coil After testing, the surface of the obtained thermoplastic elastomer physical foaming coil is smooth and smooth, with a thickness of 0.9mm, a length of 52m, a density of 0.3g/cm 3 , and uniform foam cells.
  • the average size of the foam cells in the core layer is about 21.4 ⁇ m, Shore hardness is 40C.
  • thermoplastic elastomer physical foaming coil of the present invention comprises the following steps:
  • thermoplastic elastomer coil material obtained in step (1) into a high-pressure vessel filled with N2 fluid and impregnate to obtain a high-pressure fluid content of 4% impregnated thermoplastic elastomer coil material, and then move the impregnated thermoplastic elastomer coil material into
  • the cooling chamber uses liquid nitrogen for rapid freezing and air lock treatment. At this time, the temperature in the cooling chamber is -60°C, and then stored at -20°C for 6 hours at low temperature. After 6 hours of low temperature storage, impregnate the high-pressure fluid in the thermoplastic elastomer physical foaming coil The content is 3.8%, and the mass weight loss rate of high-pressure fluid is 5%;
  • thermoplastic elastomer physical foaming roll material stored at low temperature into the heating medium and heat it for physical foaming, after rolling, cooling, and winding, the thermoplastic elastomer physical foaming roll is obtained material.
  • thermoplastic elastomer physical foaming coil After testing, the surface of the obtained thermoplastic elastomer physical foaming coil is smooth and smooth, with a thickness of 1.5mm, a length of 85m, a density of 0.1g/cm 3 , and uniform foam cells.
  • the average size of the foam cells in the core layer is about 15.5 ⁇ m, Shore hardness is 24C.
  • thermoplastic elastomer physical foaming coil of the present invention comprises the following steps:
  • thermoplastic elastomer coil material obtained in step (1) into a high-pressure container filled with CO2 fluid and impregnate to obtain a high-pressure fluid content of 9% impregnated thermoplastic elastomer coil material, and then move the impregnated thermoplastic elastomer coil material into
  • the cooling chamber adopts liquid nitrogen for rapid freezing and air lock treatment. At this time, the temperature in the cooling chamber is -60°C, and then stored at -20°C for 6 hours at low temperature. After 6 hours of low temperature storage, impregnate the high-pressure fluid in the thermoplastic elastomer physical foaming coil The content is 8.5%, and the mass weight loss rate of high-pressure fluid is 5.6%;
  • thermoplastic elastomer physical foaming roll material stored at low temperature into the heating medium and heat it for physical foaming, after rolling, cooling, and winding, the thermoplastic elastomer physical foaming roll is obtained material.
  • thermoplastic elastomer physical foaming coil After testing, the surface of the obtained thermoplastic elastomer physical foaming coil is smooth and smooth, with a thickness of 1.5mm, a length of 85m, a density of 0.1g/cm 3 , and uniform foam cells.
  • the average size of the foam cells in the core layer is about 15.5 ⁇ m, Shore hardness is 26C.
  • the blending of PVOH as a gas-phase barrier agent can further reduce the desorption rate of high-pressure fluid in the impregnated coil, so that the subsequent rapid freezing and air-locking treatment and low-temperature storage of the product can be improved. The mass loss is smaller and the resulting product has a lower density.
  • thermoplastic elastomer physical foaming coil of the present invention comprises the following steps:
  • thermoplastic elastomer coil material obtained in step (1) into a high-pressure container filled with CO2 fluid and impregnate to obtain a high-pressure fluid content of 9% impregnated thermoplastic elastomer coil material, and then move the impregnated thermoplastic elastomer coil material into
  • the cooling chamber adopts liquid nitrogen for rapid freezing and air lock treatment. At this time, the temperature in the cooling chamber is -60°C, and then stored at -20°C for 6 hours at low temperature. After 6 hours of low temperature storage, impregnate the high-pressure fluid in the thermoplastic elastomer physical foaming coil The content is 8.7%, and the mass weight loss rate of high-pressure fluid is 3.3%;
  • thermoplastic elastomer physical foaming roll material stored at low temperature into the heating medium and heat it for physical foaming, after rolling, cooling, and winding, the thermoplastic elastomer physical foaming roll is obtained material.
  • thermoplastic elastomer physical foaming coil After testing, the surface of the obtained thermoplastic elastomer physical foaming coil is smooth and smooth, with a thickness of 1.5mm, a length of 85m, a density of 0.1g/cm 3 , and uniform foam cells.
  • the average size of the foam cells in the core layer is about 35.2 ⁇ m, Shore hardness is 23C.
  • the modified coating of the PVA coating can further reduce the desorption rate of the high-pressure fluid in the impregnated coil, so that the subsequent rapid freezing and air-locking treatment and low-temperature storage of the product The weight loss of the product is smaller, and the product density is lower.
  • thermoplastic elastomer physical foaming coil of the present invention comprises the following steps:
  • step (2) Place the precursor thermoplastic elastomer coil material obtained in step (1) into a high-pressure container filled with CO2 fluid and impregnate to obtain a high-pressure fluid content of 9% impregnated thermoplastic elastomer coil material, and then move the impregnated thermoplastic elastomer coil material into
  • the cooling chamber adopts dry ice for rapid freezing and air-locking treatment. At this time, the temperature in the cooling chamber is -20°C, and then stored at -20°C for 1 hour at low temperature. The content is 8.5%, and the mass weight loss rate of high-pressure fluid is 5.6%;
  • thermoplastic elastomer physical foaming roll material stored at low temperature into the heating medium and heat it for physical foaming, after rolling, cooling, and winding, the thermoplastic elastomer physical foaming roll is obtained material.
  • thermoplastic elastomer physical foaming coil has a smooth surface, a thickness of 2 mm, a length of 92 m, a density of 0.08 g/cm 3 , and uniform foam cells.
  • the average size of the foam cells in the core layer is about 68.5 ⁇ m, the Shore hardness is 21C.
  • thermoplastic elastomer physical foaming coil of the present invention comprises the following steps:
  • thermoplastic elastomer coil material obtained in step (1) into a high-pressure container filled with CO2 fluid and impregnate to obtain a high-pressure fluid content of 9% impregnated thermoplastic elastomer coil material, and then move the impregnated thermoplastic elastomer coil material into
  • the cooling chamber adopts liquid nitrogen for rapid freezing and air lock treatment. At this time, the temperature in the cooling chamber is -100°C, and then stored at -20°C for 1 hour at low temperature. After 1 hour of low temperature storage, impregnate the high-pressure fluid in the thermoplastic elastomer physical foaming coil The content is 8.8%, and the mass weight loss rate of high-pressure fluid is 2.2%;
  • thermoplastic elastomer physical foaming roll material stored at low temperature into the heating medium and heat it for physical foaming, after rolling, cooling, and winding, the thermoplastic elastomer physical foaming roll is obtained material.
  • thermoplastic elastomer physical foaming coil After testing, the surface of the obtained thermoplastic elastomer physical foaming coil is smooth and smooth, with a thickness of 2.2mm, a length of 95m, a density of 0.075g/cm 3 , and uniform foam cells.
  • the average size of the foam cells in the core layer is about 72.6 ⁇ m, Shore hardness is 20C.
  • thermoplastic elastomer physical foaming coil of the present invention comprises the following steps:
  • TPU particles (Shore hardness is 95A)
  • talc powder 5 parts of talc powder and 0.5 parts of antioxidant are sequentially dried, pre-mixed, twin-screw continuous extrusion, calendered and rolled to obtain a precursor with a thickness of 1mm. Thermoplastic elastomer rolls;
  • thermoplastic elastomer coil material obtained in step (1) into a high-pressure container filled with CO2 fluid and impregnate to obtain a high-pressure fluid content of 9% impregnated thermoplastic elastomer coil material, and then move the impregnated thermoplastic elastomer coil material into
  • the cooling chamber adopts liquid nitrogen for rapid freezing and air-locking treatment. At this time, the temperature in the cooling chamber is -60°C, and then stored at -20°C for 1 hour at low temperature. After 1 hour of low temperature storage, impregnate the high-pressure fluid in the thermoplastic elastomer physical foaming coil The content is 6.7%, and the mass weight loss rate of high-pressure fluid is 4.3%;
  • thermoplastic elastomer physical foaming roll material stored at low temperature into the heating medium and heat it for physical foaming, after rolling, cooling, and winding, the thermoplastic elastomer physical foaming roll is obtained material.
  • thermoplastic elastomer physical foaming coil has a smooth surface, a thickness of 1.4mm, a length of 56m, a density of 0.38g/cm 3 , and uniform foam cells.
  • the average size of the foam cells in the core layer is about 26.8 ⁇ m, Shore hardness is 45C.
  • thermoplastic elastomer physical foam coil comprising the following steps:
  • step (2) Place the precursor thermoplastic elastomer coil material obtained in step (1) into a high-pressure container filled with CO2 fluid and impregnate to obtain an impregnated thermoplastic elastomer coil material with a high-pressure fluid content of 9%, and then place it at normal temperature and pressure for 10 minutes;
  • thermoplastic elastomer physical foaming coil Pass the impregnated thermoplastic elastomer physical foaming coil into a heating medium and heat to perform physical foaming.
  • thermoplastic elastomer physical foam coil comprising the following steps:
  • TPU particles (Shore hardness is 80A)
  • 10 parts of PVOH and 0.5 parts of antioxidant are sequentially dried, pre-mixed, twin-screw continuous extrusion, calendered and rolled to obtain a precursor thermoplastic with a thickness of 1mm. Elastomer rolls;
  • step (2) Place the precursor thermoplastic elastomer coil material obtained in step (1) into a high-pressure container filled with CO2 fluid and impregnate to obtain an impregnated thermoplastic elastomer coil material with a high-pressure fluid content of 9%, and then place it at normal temperature and pressure for 10 minutes;
  • thermoplastic elastomer physical foaming coil Pass the impregnated thermoplastic elastomer physical foaming coil into a heating medium and heat to perform physical foaming.
  • thermoplastic elastomer physical foam coil comprising the following steps:
  • thermoplastic elastomer roll material 100 parts of TPU particles (Shore hardness is 80A), 10 parts of EVA particles and 0.5 parts of antioxidant are sequentially dried, pre-mixed, twin-screw continuous extrusion, calendering, PVA aqueous solution coating modification (PVA aqueous solution The mass content of PVA in the medium is 18%, and the PVA coating thickness of described coating modification is 0.03mm), after drying and winding, obtain the precursor thermoplastic elastomer roll material that thickness is 0.3mm;
  • step (2) Place the precursor thermoplastic elastomer coil material obtained in step (1) into a high-pressure container filled with CO2 fluid and impregnate to obtain an impregnated thermoplastic elastomer coil material with a high-pressure fluid content of 9%, and then place it at normal temperature and pressure for 10 minutes;
  • thermoplastic elastomer physical foaming coil Pass the impregnated thermoplastic elastomer physical foaming coil into a heating medium and heat to perform physical foaming.
  • Example 2 Compared with the product obtained in Example 6, it can be seen that the impregnated coils that have not been subjected to rapid freezing and air-locking treatment and low-temperature storage cannot imprison high-pressure fluids. Even if PVA coatings are used to reduce the desorption rate of high-pressure fluids, the final effect is not good. The fluid will still escape the TPU matrix, making it difficult for the product to foam stably.
  • thermoplastic elastomer physical foam coil comprising the following steps:
  • thermoplastic elastomer coil material obtained in step (1) into a high-pressure container filled with CO2 fluid and impregnate to obtain a high-pressure fluid content of 9% impregnated thermoplastic elastomer coil material, and then move the impregnated thermoplastic elastomer coil material into
  • the cooling chamber adopts liquid nitrogen for rapid freezing and air lock treatment. At this time, the temperature in the cooling chamber is -10°C, and then stored at -20°C for 6 hours at low temperature. After 6 hours of low temperature storage, impregnate the high-pressure fluid in the thermoplastic elastomer physical foaming coil The content is 6%, and the mass weight loss rate of high-pressure fluid is 33.3%;
  • thermoplastic elastomer physical foaming roll material stored at low temperature into the heating medium and heat it for physical foaming, after rolling, cooling, and winding, the thermoplastic elastomer physical foaming roll is obtained material.
  • thermoplastic elastomer physical foaming coil After testing, compared with the product obtained in Example 2, the obtained thermoplastic elastomer physical foaming coil has a flat surface, a thickness of 1.3 mm, a length of 52 m, and a density of 0.3 g/cm 3 increased to 0.6 g/cm 3 , The average size of the foamed cells in the core layer is about 85.6 ⁇ m, and the Shore hardness is 45C.

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Abstract

本发明公开了一种热塑性弹性体物理发泡卷材及其半连续制备方法，属于热塑性弹性体发泡革领域。本发明所述热塑性弹性体物理发泡卷材的半连续制备方法中，通过控制高压流体在热塑性弹性体卷材中的溶解度含量，随后在特定温度下对材料进行快速冷冻锁气处理，抑制高压流体的解吸附现象，所得浸渍卷材可在低温下长时间储存或进行远程运输，同时可稳定地进行连续升温发泡，且无论在储存或者发泡过程中均不会如现有技术一样发生明显的高压流体逃逸，可实施性显著提高；该方法可实现大规模连续生产，安全环保。本发明还公开了所述制备方法制备的热塑性弹性体物理发泡卷材，该产品厚度为0.1～3mm，密度为0.1～0.6g/cm 3，发泡泡孔的尺寸为1～200μm，邵氏硬度为20～60C。

Description

一种热塑性弹性体物理发泡卷材及其半连续制备方法 技术领域
本发明涉及热塑性弹性体发泡革领域，具体涉及一种热塑性弹性体物理发泡卷材及其半连续制备方法。
背景技术
一般聚合物发泡革(如PVC革、PU革等)在加工过程中涉及大量氯化物、硫化物、溶剂、增塑剂的使用和排放，存在产品VOC释放问题，在汽车沙发革、内饰革等领域应用受限。
热塑弹性体如热塑性聚氨酯(TPU)、聚酯弹性体(TPEE)、尼龙弹性体(TPAE)是一类相比传统聚合物更加环保友好的材料，同时它具有优异的耐磨性、耐刮差性、机械强度性、透气性、耐水耐油性、耐菌性以及可进行熔融回收等特点。典型的，采用TPU树脂来制备的TPU发泡薄膜是一种具有广泛应用前景的人造革材料。
CN111484725A、CN108285634A均公开了TPU发泡皮革及其制备工艺，这些产品的制备方案中使用了AC发泡剂、微球发泡剂或者上述发泡剂的复合物作为添加剂，通过挤出压延的工艺来制备TPU发泡膜。然而AC发泡剂和微球发泡剂在加工过程中存在分解不完全的问题，容易导致环保问题；同时，采用化学发泡剂制备TPU发泡革的还存在产品发泡泡孔尺寸大、发泡膨胀倍率低的问题。
CN105714574B公开了一种超临界流体连续挤出发泡发泡TPU人造革的制备方法，该方案在第一挤出机中连续熔融TPU树脂，在第一挤出机的末端注入超临界流体如CO 2流体，经熔体泵将聚合物/流体混合物注入到第二挤出机中，经第二挤出机摸头流延制备TPU发泡膜。但是，该方案中高压流体在高温挤出 模头中扩散速度太快，高压流体易于从聚合物熔体中逃逸。当挤出薄膜的厚度降低时，高压流体的逃逸程度显著提高，因此这种方法难以制备厚度低于1mm、泡孔尺寸分布均匀的TPU发泡膜；同时，高压流体的快速逃逸，也导致发泡薄膜表面存在气纹、波浪纹等表面缺陷。
为了制备厚度更薄的TPU发泡革，如厚度为0.3～2.0mm的产品，CN104611942B公开了一种超临界N 2流体连续挤出发泡制备发泡革的方法。这种方法虽然可以制备低厚度产品，然而在制备过程中N 2在TPU中的溶解度较低，制备的TPU发泡革的密度一般为0.4～0.8g/cm 3，存在密度较大的问题。同时，连续挤出发泡过程中依然存在高压流体在高温下容易逃逸的问题，导致发泡薄膜产品表皮存在气纹、波浪纹等缺陷。
经过探索研究，人们发现采用釜压发泡可以制备表面光洁、泡孔尺寸小、泡孔结构分布均匀且密度低的TPU发泡薄膜。CN103951965B公开了一种TPU发泡片材的制备方法，该方法将高压流体浸渍彩色TPU片材，然后将彩色TPU片材置于水浴中加热发泡，最终得到彩色TPU发泡片材。然而高压流体在常温常压下依然会扩散逃逸出浸渍TPU片材，导致高压流体浸渍TPU片材在常温常压放置一段时间后就不能发泡。因此，这个技术难以稳定、连续地制备TPU发泡卷材。同时，作为行业共知的，当TPU薄膜的厚度低于0.1mm时，高压流体会快速逃逸出浸渍TPU薄膜，导致浸渍TPU发泡薄膜难以进行升温发泡。
为了解决上述难题，CN108479431B公开了一种将两层气体阻隔膜和TPU薄膜复合成三明治结构的方法，由于气体阻隔膜可以阻碍高压流体从浸渍TPU膜中逃逸出去，从而可以制备厚度低于0.1mm的TPU薄膜。但是，现有文献存在报道说明，阻隔膜与TPU膜的界面粘附强度会影响TPU的发泡行为，导致不同的膨胀行为和泡孔形态，因此采用气体阻隔膜改善TPU薄膜发泡的技术在大规模实施过程中存在难题。同时，阻隔膜的价格高昂，使用这类原料也会导致产品加工过程成本变高。另外，高压流体发泡剂浸渍的TPU薄膜在常温常压长时间放置时容易发生解吸附现象，大量发泡剂的逃逸导致TPU发泡过程不稳定，也限制TPU发泡薄膜卷材的大规模制备。
发明内容
基于现有技术存在的缺陷，本发明的目的在于提供一种热塑性弹性体物理发泡卷材的半连续制备方法，该方法将热塑性弹性体卷材在高压流体浸渍后进行快速冷冻锁气处理，不仅使浸渍卷材在发泡过程中不会发生明显减重，高压流体在卷材中的逃逸率显著降低，同时可实现卷材的远距离运输及连续升温发泡；该方法可实现大规模连续生产，安全环保，所得产品表面光洁，厚度较薄，密度低且发泡泡孔微小、均匀一致。
为了达到上述目的，本发明采取的技术方案为：
一种热塑性弹性体物理发泡卷材的半连续制备方法，包括以下步骤：
(1)将热塑性弹性体和助剂依次经干燥、预混合、双螺杆连续挤出、压延和收卷后，得前驱热塑性弹性体卷材；
(2)将步骤(1)所得前驱热塑性弹性体卷材置入高压流体中浸渍得到浸渍热塑性弹性体卷材，随后将浸渍热塑性弹性体卷材进行快速冷冻锁气处理并低温储存；所述浸渍热塑性弹性体卷材中高压流体的质量含量为1～15％；所述快速冷冻锁气处理的温度为-20～-100℃；所述低温储存的温度为-60～-20℃；
(3)将低温储存的浸渍热塑性弹性体卷材通入加热介质中并加热进行物理发泡后，经辊压、冷却、收卷后，即得所述热塑性弹性体物理发泡卷材；所述加热介质为热空气或热水。
经过高压流体浸渍热塑性弹性体卷材在快速冷冻锁气处理后，弹性体聚酯的分子链的运动被冻结，进而高压流体分子的运动也被连带最大限度地禁锢，使得浸渍后的热塑性弹性体卷材可在特定低温下长时间储存或者运输，在储存及后续发泡过程中高压流体分子的解吸速率显著降低，有利于保持热塑性弹性体卷材的失重率。
而发明人多次实验筛选后，发现当浸渍后的热塑性弹性体卷材在-20～-100℃时进行冷冻锁气处理时其效果及实施可行性最高：当温度低于-100℃时对高压流体的分子禁锢率提升不高，同时对设备要求提高，成本显著提升，而当温度高 于-20℃时，高压流体分子运动概率提升，又会无法保障优选的失重率。
本发明所述热塑性弹性体物理发泡卷材的制备方法中，通过控制高压流体在热塑性弹性体卷材中的溶解度含量，随后在特定温度下对材料进行快速冷冻锁气处理，抑制高压流体的解吸附现象，所得浸渍卷材可在低温下长时间储存或进行远程运输，同时可稳定地进行连续升温发泡，且无论在储存或者发泡过程中均不会如现有技术一样发生明显的高压流体逃逸，可实施性显著提高；该方法可实现大规模连续生产，安全环保，制备所得产品表面光洁，厚度较薄，密度低且发泡泡孔微小、均匀一致。
优选地，步骤(1)所述热塑性弹性体的邵氏硬度为60～95A，所述前驱热塑性弹性体卷材的厚度为0.1～3mm。
通过优选特定的原料硬度以及前驱体厚度，可保障后续高压流体的浸渍、发泡效果以及最终产品的性能，避免厚度不理想导致高压流体浸渍率过高或过低，发泡效果不佳；或者因硬度不足导致产品力学性能不佳。
优选地，步骤(1)所述热塑性弹性体包括TPU、TPEE、TPAE中的至少一种，所述助剂包括成核剂和抗氧剂；
更优选地，步骤(1)所述热塑性弹性体的添加重量份数为100份，所述成核剂的添加重量份数为0～20份，所述抗氧剂的添加重量份数为0～1份。
当添加特定含量的抗氧剂以及成核剂后，所得热塑性弹性体的稳定性更高，同时可优化热塑性弹性体卷材在浸渍高压流体后的结晶度，进一步抑制浸渍卷材在储存和发泡过程中的失重现象。
优选地，步骤(1)所述100份热塑性弹性体中，所述TPU的重量份数为1～99份；更优选地，所述TPU的重量份数为5～30份或70～95份。
TPU、TPEE、TPAE的玻璃化温度为约-30～-50℃，而三者的硬度等性质均较为接近，三者的添加量配比可根据实际进行生产进行调整，制备浸渍率高且发泡平整的热塑性弹性体卷材。
优选地，所述成核剂包括有机成核剂和无机成核剂，所述有机成核剂包括EVA、POE、OBC、SBES、EPDM中的至少一种，所述无机成核剂包括碳酸钙、 滑石粉、云母、玻璃微珠中的至少一种。
优选地，步骤(1)所述助剂还包括1～20份的气体阻隔剂。
相比于一般聚合物聚酯，热塑性弹性体中的分子扩散运动频率更高，相比于一般发泡材料其在发泡过程中更容易发生气体逃逸现象，导致发泡效率显著降低。通过添加适当的气体阻隔剂可在热塑性弹性体卷材中形成致密的交联网络，有效禁锢浸渍后的高压流体，降低高压流体的解吸附速率。
更优选地，所述气体阻隔剂包括PVOH、PVA中的至少一种；
更优选地，所述气体阻隔剂为PVOH。
优选地，步骤(1)所述前驱热塑性弹性体卷材还含有气体阻隔层，所述前驱热塑性弹性体卷材的制备方法为：将热塑性弹性体和助剂依次经干燥、预混合、双螺杆连续挤出、压延后，在弹性体表面涂覆含有PVA的水溶液，再经过干燥及收卷，得前驱热塑性弹性体卷材。
与上述添加气体阻隔剂相似，当前驱热塑性弹性体卷材在制备过程中采用PVA水溶液进行涂覆改性，当干燥后，形成的PVA薄膜同样可以抑制高压流体在储存及发泡过程中的逃逸；而由于本发明所述制备方法包含快速冷冻锁气处理，相比于现有技术该PVA薄膜可保障高压流体的低解吸附性，同时所述薄膜与热塑性弹性体相容性高，不会导致明显的膨胀及泡孔形态差异性；该改性涂覆及干燥步骤简单易施行，不会造成加工成本提高。
优选地，所述气体阻隔层的厚度为0.01～0.05mm。
优选地，所述PVA的水溶液中PVA的质量含量为5～30％；
更优选地，所述PVA的水溶液中PVA的质量含量为10～20％。
优选地，步骤(2)所述高压流体包括CO 2流体、N 2流体中的至少一种。
更优选地，步骤(2)所述浸渍时的高压流体的压力为1～7MPa，所述浸渍的时间为1～24h。
优选地，步骤(2)所述浸渍后得到的浸渍热塑性弹性体卷材中高压流体的质量含量为2～10％。
本发明所述高压流体在热塑性弹性体卷材中的含量(％)＝(m 1-m 0)× 100％/m 0；其中m 0为前驱热塑性弹性体卷材的质量，m 1为高压流体浸渍后，常温常压解吸附10min之后的浸渍热塑性弹性体卷材的质量。通过对高压流体的浸渍含量进行优选，可进一步控制后续产品的结晶度、密度及发泡效率等性质。
优选地，步骤(2)所述快速冷冻锁气处理采用液氮或者干冰进行。
液氮的沸点为-196℃，而干冰则是-57℃，两种均是环保且廉价的工业制冷剂，采用这两种物质对浸渍高压流体进行瞬间冷冻处理具有高效、实施成本低的特点。
优选地，步骤(2)所述快速冷冻锁气处理的温度为-50～-80℃。
由于热塑性弹性体在-30～-50℃下已经发生玻璃化现象，因此当温度维持在上述优选范围内时已经足够限制高压流体的运动逃逸，当温度继续降低时其限制效果提升量不大，且会提高生产成本及难度。
优选地，步骤(3)所述低温储存的浸渍热塑性弹性体卷材的质量失重为0～50％/天；
更优选地，所述低温储存的浸渍热塑性弹性体卷材的质量失重为5～30％/天；
更优选地，所述低温储存的浸渍热塑性弹性体卷材的质量失重为5～20％/天；
更优选地，所述低温储存的浸渍热塑性弹性体卷材的质量失重为5～10％/天。
通过本发明所述快速冷冻锁气处理后，高压流体被限制在热塑性弹性体卷材中，失重速率显著降低，在特定条件下，所述浸渍热塑性弹性体卷材的失重率最低可达到5～10％/每天。
所述低温储存的浸渍热塑性弹性体卷材的质量失重率(％)＝(m 1-m 2)×100％/(m 1-m 0)；
其中，m 0为前驱热塑性弹性体卷材的质量，m 1为高压流体浸渍后、常温常压解吸附10min之后的浸渍热塑性弹性体卷材的质量，m 2为浸渍热塑性弹性体卷材经冷冻锁气和低温存储后，常温常压解吸附10min之后的浸渍后的热塑性弹性体卷材的质量。
本发明的另一目的还在于提供所述热塑性弹性体物理发泡卷材的半连续制备方法制备的热塑性弹性体物理发泡卷材，所述热塑性弹性体物理发泡卷材在 发泡前经过快速冷冻锁气及低温储存处理，所述热塑性弹性体物理发泡卷材的厚度为0.1～3mm，密度为0.1～0.6g/cm 3，发泡泡孔的尺寸为1～200μm，邵氏硬度为20～60C。
本发明所提供的聚酯发泡卷材产品相比于现有技术所得产品，由于经过特殊处理抑制了高压流体的逃逸，具有更薄的厚度(可低于0.1mm)，更低的密度，而产品的发泡过程平稳均匀，发泡后表面平整光滑，质量较高，且具有优异的力学性能。
优选地，所述热塑性弹性体物理发泡卷材的厚度为0.5～2mm。
更优选地，所述热塑性弹性体物理发泡卷材包括不发泡皮层及其内部的发泡芯层，所述发泡芯层中发泡泡孔的尺寸为10～50μm。
优选地，所述热塑性弹性体物理发泡卷材的长度≥50m。
由于发泡的连续平稳性，所得产品可保留完整理想的长度，适配于各种应用领域。
本发明的有益效果在于，本发明提供了一种所述热塑性弹性体物理发泡卷材的半连续制备方法中，通过控制高压流体在热塑性弹性体卷材中的溶解度含量，随后在特定温度下对材料进行快速冷冻锁气处理，抑制高压流体的解吸附现象，所得浸渍卷材可在低温下长时间储存或进行远程运输，同时可稳定地进行连续升温发泡，且无论在储存或者发泡过程中均不会如现有技术一样发生明显的高压流体逃逸，可实施性显著提高；该方法可实现大规模连续生产，安全环保。本发明还提供了所述制备方法制备的热塑性弹性体物理发泡卷材，该产品厚度为0.1～3mm，密度为0.1～0.6g/cm 3，发泡泡孔的尺寸为1～200μm，邵氏硬度为20～60C。
附图说明
图1为本发明所述热塑性弹性体物理发泡卷材的光学照片；
图2为本发明所述热塑性弹性体物理发泡卷材的断面扫描电镜图。
具体实施方式
为了更好地说明本发明的目的、技术方案和优点，下面将结合具体实施例及对比例对本发明作进一步说明，其目的在于详细地理解本发明的内容，而不是对本发明的限制。本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明的保护范围。本发明实施所设计的实验试剂及仪器，除非特别说明，均为常用的普通试剂及仪器。
其中，各实施例及对比例中经过快速冷冻锁气处理及低温储存的浸渍聚酯卷材中高压流体含量(％)＝(m 2-m 0)×100％/m 0；
m 0为前驱热塑性弹性体卷材的质量，m 2为浸渍的热塑性弹性体卷材经快速冷冻锁气处理和低温存储后，常温常压解吸附10min之后的浸渍的热塑性弹性体卷材的质量。
实施例1
本发明所述热塑性弹性体物理发泡卷材的半连续制备方法的实施例，包括以下步骤：
(1)将100份TPU颗粒(邵氏硬度为80A)、5份滑石粉和0.5份抗氧剂依次经干燥、预混合、双螺杆连续挤出、压延和收卷后，得厚度为1mm前驱热塑性弹性体卷材；
(2)将步骤(1)所得前驱热塑性弹性体卷材置入充满CO 2流体的高压容器中浸渍得到高压流体含量为9％的浸渍热塑性弹性体卷材，随后将浸渍热塑性弹性体卷材移入冷却腔采用液氮进行快速冷冻锁气处理，此时冷却腔内的温度为-60℃，再在-20℃下低温储存1h，低温储存1h后浸渍热塑性弹性体物理发泡卷材中高压流体的含量为8.2％，高压流体的质量失重率为8.9％；
(3)将低温储存的浸渍热塑性弹性体物理发泡卷材通入加热介质中并加热进行物理发泡后，经辊压、冷却、收卷后，即得所述热塑性弹性体物理发泡卷材。
经检测，如图1所示，所得热塑性弹性体物理发泡卷材的表面光洁平整， 厚度为0.5mm，长度为60m，密度为0.2g/cm 3，发泡泡孔均匀，如图2所示，芯层发泡泡孔平均尺寸约为25.8μm，邵氏硬度为30C。
实施例2
本发明所述热塑性弹性体物理发泡卷材的半连续制备方法的实施例，包括以下步骤：
(1)将100份TPU颗粒(邵氏硬度为80A)、10份EVA颗粒和0.5份抗氧剂依次经干燥、预混合、双螺杆连续挤出、压延和收卷后，得厚度为0.3mm前驱热塑性弹性体卷材；
(2)将步骤(1)所得前驱热塑性弹性体卷材置入充满CO 2流体的高压容器中浸渍得到高压流体含量为9％的浸渍热塑性弹性体卷材，随后将浸渍热塑性弹性体卷材移入冷却腔采用液氮进行快速冷冻锁气处理，此时冷却腔内的温度为-60℃，再在-20℃下低温储存6h，低温储存6h后浸渍热塑性弹性体物理发泡卷材中高压流体的含量为7.8％，高压流体的质量失重率为13.3％；
(3)将低温储存的浸渍热塑性弹性体物理发泡卷材通入加热介质中并加热进行物理发泡后，经辊压、冷却、收卷后，即得所述热塑性弹性体物理发泡卷材。
经检测，所得热塑性弹性体物理发泡卷材的表面光洁平整，厚度为1.5mm，长度为58m，密度为0.3g/cm 3，发泡泡孔均匀，芯层发泡泡孔平均尺寸约为30.4μm，邵氏硬度为38C。
实施例3
本发明所述热塑性弹性体物理发泡卷材的半连续制备方法的实施例，包括以下步骤：
(1)将100份TPEE颗粒(邵氏硬度为85A)、0.5份抗氧剂依次经干燥、预混合、双螺杆连续挤出、压延和收卷后，得厚度为0.5mm前驱热塑性弹性体卷材；
(2)将步骤(1)所得前驱热塑性弹性体卷材置入充满CO 2流体的高压容器中浸渍得到高压流体含量为8.5％的浸渍热塑性弹性体卷材，随后将浸渍热塑 性弹性体卷材移入冷却腔采用液氮进行快速冷冻锁气处理，此时冷却腔内的温度为-60℃，再在-20℃下低温储存24h，低温储存24h后浸渍热塑性弹性体物理发泡卷材中高压流体的含量为6.5％，高压流体的质量失重率为23.5％；
(3)将低温储存的浸渍热塑性弹性体物理发泡卷材通入加热介质中并加热进行物理发泡后，经辊压、冷却、收卷后，即得所述热塑性弹性体物理发泡卷材。
经检测，所得热塑性弹性体物理发泡卷材的表面光洁平整，厚度为0.9mm，长度为52m，密度为0.3g/cm 3，发泡泡孔均匀，芯层发泡泡孔平均尺寸约为21.4μm，邵氏硬度为40C。
实施例4
本发明所述热塑性弹性体物理发泡卷材的半连续制备方法的实施例，包括以下步骤：
(1)将100份TPU颗粒(邵氏硬度为80A)、5份滑石粉和0.5份抗氧剂依次经干燥、预混合、双螺杆连续挤出、压延和收卷后，得厚度为1mm前驱热塑性弹性体卷材；
(2)将步骤(1)所得前驱热塑性弹性体卷材置入充满N 2流体的高压容器中浸渍得到高压流体含量为4％的浸渍热塑性弹性体卷材，随后将浸渍热塑性弹性体卷材移入冷却腔采用液氮进行快速冷冻锁气处理，此时冷却腔内的温度为-60℃，再在-20℃下低温储存6h，低温储存6h后浸渍热塑性弹性体物理发泡卷材中高压流体的含量为3.8％，高压流体的质量失重率为5％；
(3)将低温储存的浸渍热塑性弹性体物理发泡卷材通入加热介质中并加热进行物理发泡后，经辊压、冷却、收卷后，即得所述热塑性弹性体物理发泡卷材。
经检测，所得热塑性弹性体物理发泡卷材的表面光洁平整，厚度为1.5mm，长度为85m，密度为0.1g/cm 3，发泡泡孔均匀，芯层发泡泡孔平均尺寸约为15.5μm，邵氏硬度为24C。经过与实施例2所述制备方法及产品密度对比表明，N2浸渍后的热塑性弹性体卷材中N 2的解吸附速率比CO 2低，在后续快速冷冻锁气 处理及低温储存的质量失重更小，得到的产品密度更低。
实施例5
本发明所述热塑性弹性体物理发泡卷材的半连续制备方法的实施例，包括以下步骤：
(1)将100份TPU颗粒(邵氏硬度为80A)、10份PVOH和0.5份抗氧剂依次经干燥、预混合、双螺杆连续挤出、压延和收卷后，得厚度为0.3mm前驱热塑性弹性体卷材；
(2)将步骤(1)所得前驱热塑性弹性体卷材置入充满CO 2流体的高压容器中浸渍得到高压流体含量为9％的浸渍热塑性弹性体卷材，随后将浸渍热塑性弹性体卷材移入冷却腔采用液氮进行快速冷冻锁气处理，此时冷却腔内的温度为-60℃，再在-20℃下低温储存6h，低温储存6h后浸渍热塑性弹性体物理发泡卷材中高压流体的含量为8.5％，高压流体的质量失重率为5.6％；
(3)将低温储存的浸渍热塑性弹性体物理发泡卷材通入加热介质中并加热进行物理发泡后，经辊压、冷却、收卷后，即得所述热塑性弹性体物理发泡卷材。
经检测，所得热塑性弹性体物理发泡卷材的表面光洁平整，厚度为1.5mm，长度为85m，密度为0.1g/cm 3，发泡泡孔均匀，芯层发泡泡孔平均尺寸约为15.5μm，邵氏硬度为26C。经过与实施例2所述制备方法及产品密度对比表明，PVOH作为气相阻隔剂共混可以进一步降低高压流体在浸渍卷材中的解吸附速率，使其产品后续快速冷冻锁气处理及低温储存的质量失重更小，得到的产品密度更低。
实施例6
本发明所述热塑性弹性体物理发泡卷材的半连续制备方法的实施例，包括以下步骤：
(1)将100份TPU颗粒(邵氏硬度为80A)、10份EVA颗粒和0.5份抗氧剂依次经干燥、预混合、双螺杆连续挤出、压延，PVA水溶液涂覆改性(PVA水溶液中PVA的质量含量为18％，所述涂覆改性的PVA涂层厚度为0.03mm)、 干燥及收卷后，得厚度为0.3mm前驱热塑性弹性体卷材；
(2)将步骤(1)所得前驱热塑性弹性体卷材置入充满CO 2流体的高压容器中浸渍得到高压流体含量为9％的浸渍热塑性弹性体卷材，随后将浸渍热塑性弹性体卷材移入冷却腔采用液氮进行快速冷冻锁气处理，此时冷却腔内的温度为-60℃，再在-20℃下低温储存6h，低温储存6h后浸渍热塑性弹性体物理发泡卷材中高压流体的含量为8.7％，高压流体的质量失重率为3.3％；
(3)将低温储存的浸渍热塑性弹性体物理发泡卷材通入加热介质中并加热进行物理发泡后，经辊压、冷却、收卷后，即得所述热塑性弹性体物理发泡卷材。
经检测，所得热塑性弹性体物理发泡卷材的表面光洁平整，厚度为1.5mm，长度为85m，密度为0.1g/cm 3，发泡泡孔均匀，芯层发泡泡孔平均尺寸约为35.2μm，邵氏硬度为23C。经过与实施例2所述制备方法及产品密度对比表明，PVA涂层的改性涂覆可以进一步降低高压流体在浸渍卷材中的解吸附速率，使其产品后续快速冷冻锁气处理及低温储存的质量失重更小，得到的产品密度更低。
实施例7
本发明所述热塑性弹性体物理发泡卷材的半连续制备方法的实施例，包括以下步骤：
(1)将100份TPU颗粒(邵氏硬度为80A)、5份滑石粉和0.5份抗氧剂依次经干燥、预混合、双螺杆连续挤出、压延和收卷后，得厚度为1mm前驱热塑性弹性体卷材；
(2)将步骤(1)所得前驱热塑性弹性体卷材置入充满CO 2流体的高压容器中浸渍得到高压流体含量为9％的浸渍热塑性弹性体卷材，随后将浸渍热塑性弹性体卷材移入冷却腔采用干冰进行快速冷冻锁气处理，此时冷却腔内的温度为-20℃，再在-20℃下低温储存1h，低温储存1h后浸渍热塑性弹性体物理发泡卷材中高压流体的含量为8.5％，高压流体的质量失重率为5.6％；
(3)将低温储存的浸渍热塑性弹性体物理发泡卷材通入加热介质中并加热进行物理发泡后，经辊压、冷却、收卷后，即得所述热塑性弹性体物理发泡卷 材。
经检测，所得热塑性弹性体物理发泡卷材的表面光洁平整，厚度为2mm，长度为92m，密度为0.08g/cm 3，发泡泡孔均匀，芯层发泡泡孔平均尺寸约为68.5μm，邵氏硬度为21C。
实施例8
本发明所述热塑性弹性体物理发泡卷材的半连续制备方法的实施例，包括以下步骤：
(1)将100份TPU颗粒(邵氏硬度为80A)、5份滑石粉和0.5份抗氧剂依次经干燥、预混合、双螺杆连续挤出、压延和收卷后，得厚度为1mm前驱热塑性弹性体卷材；
(2)将步骤(1)所得前驱热塑性弹性体卷材置入充满CO 2流体的高压容器中浸渍得到高压流体含量为9％的浸渍热塑性弹性体卷材，随后将浸渍热塑性弹性体卷材移入冷却腔采用液氮进行快速冷冻锁气处理，此时冷却腔内的温度为-100℃，再在-20℃下低温储存1h，低温储存1h后浸渍热塑性弹性体物理发泡卷材中高压流体的含量为8.8％，高压流体的质量失重率为2.2％；
(3)将低温储存的浸渍热塑性弹性体物理发泡卷材通入加热介质中并加热进行物理发泡后，经辊压、冷却、收卷后，即得所述热塑性弹性体物理发泡卷材。
经检测，所得热塑性弹性体物理发泡卷材的表面光洁平整，厚度为2.2mm，长度为95m，密度为0.075g/cm 3，发泡泡孔均匀，芯层发泡泡孔平均尺寸约为72.6μm，邵氏硬度为20C。
实施例9
本发明所述热塑性弹性体物理发泡卷材的半连续制备方法的实施例，包括以下步骤：
(1)将100份TPU颗粒(邵氏硬度为95A)、5份滑石粉和0.5份抗氧剂依次经干燥、预混合、双螺杆连续挤出、压延和收卷后，得厚度为1mm前驱热塑性弹性体卷材；
(2)将步骤(1)所得前驱热塑性弹性体卷材置入充满CO 2流体的高压容器中浸渍得到高压流体含量为9％的浸渍热塑性弹性体卷材，随后将浸渍热塑性弹性体卷材移入冷却腔采用液氮进行快速冷冻锁气处理，此时冷却腔内的温度为-60℃，再在-20℃下低温储存1h，低温储存1h后浸渍热塑性弹性体物理发泡卷材中高压流体的含量为6.7％，高压流体的质量失重率为4.3％；
(3)将低温储存的浸渍热塑性弹性体物理发泡卷材通入加热介质中并加热进行物理发泡后，经辊压、冷却、收卷后，即得所述热塑性弹性体物理发泡卷材。
经检测，所得热塑性弹性体物理发泡卷材的表面光洁平整，厚度为1.4mm，长度为56m，密度为0.38g/cm 3，发泡泡孔均匀，芯层发泡泡孔平均尺寸约为26.8μm，邵氏硬度为45C。
对比例1
一种热塑性弹性体物理发泡卷材的制备方法，包括以下步骤：
(1)将100份TPU颗粒(邵氏硬度为80A)、5份滑石粉和0.5份抗氧剂依次经干燥、预混合、双螺杆连续挤出、压延和收卷后，得厚度为1mm前驱热塑性弹性体卷材；
(2)将步骤(1)所得前驱热塑性弹性体卷材置入充满CO 2流体的高压容器中浸渍得到高压流体含量为9％的浸渍热塑性弹性体卷材，随后常温常压放置10min；
(3)将放置后的浸渍热塑性弹性体物理发泡卷材通入加热介质中并加热进行物理发泡。
最终结果发现，所述卷材无法进行均匀发泡，在常温常压放置1h后，浸渍热塑性弹性体卷材中高压流体的含量只有3.5％，高压流体的质量失重率为61.1％，剩余高压流体不足以驱动均匀的物理发泡进行，与实施例2所得产品对比可知，未经过快速冷冻锁气处理及低温储存的浸渍卷材无法禁锢高压流体，高压流体会迅速逃逸TPU基体，导致产品难以发泡。
对比例2
一种热塑性弹性体物理发泡卷材的制备方法，包括以下步骤：
(1)将100份TPU颗粒(邵氏硬度为80A)、10份PVOH和0.5份抗氧剂依次经干燥、预混合、双螺杆连续挤出、压延和收卷后，得厚度为1mm前驱热塑性弹性体卷材；
(2)将步骤(1)所得前驱热塑性弹性体卷材置入充满CO 2流体的高压容器中浸渍得到高压流体含量为9％的浸渍热塑性弹性体卷材，随后常温常压放置10min；
(3)将放置后的浸渍热塑性弹性体物理发泡卷材通入加热介质中并加热进行物理发泡。
最终结果发现，所述卷材无法进行均匀发泡，同时10m后的卷材中出现明显的不发泡区域；与实施例2和实施例5所得产品对比可知，未经过快速冷冻锁气处理及低温储存的浸渍卷材无法禁锢高压流体，即使采用PVOH用于降低高压流体的解吸附速率，其最终效果不佳，高压流体依然会逃逸TPU基体，导致产品难以稳定发泡。
对比例3
一种热塑性弹性体物理发泡卷材的制备方法，包括以下步骤：
(1)将100份TPU颗粒(邵氏硬度为80A)、10份EVA颗粒和0.5份抗氧剂依次经干燥、预混合、双螺杆连续挤出、压延、PVA水溶液涂覆改性(PVA水溶液中PVA的质量含量为18％，所述涂覆改性的PVA涂层厚度为0.03mm)、干燥及收卷后，得厚度为0.3mm前驱热塑性弹性体卷材；
(2)将步骤(1)所得前驱热塑性弹性体卷材置入充满CO 2流体的高压容器中浸渍得到高压流体含量为9％的浸渍热塑性弹性体卷材，随后常温常压放置10min；
(3)将放置后的浸渍热塑性弹性体物理发泡卷材通入加热介质中并加热进行物理发泡。
最终结果发现，所述卷材可以发生均匀的发泡膨胀，同时10m后的卷材中的发泡提及膨胀不再均匀，再10m后的卷材出现明显不发泡区域；与实施例2 和实施例6所得产品对比可知，未经过快速冷冻锁气处理及低温储存的浸渍卷材无法禁锢高压流体，即使采用PVA涂层用于降低高压流体的解吸附速率，其最终效果不佳，高压流体依然会逃逸TPU基体，导致产品难以稳定发泡。
对比例4
一种热塑性弹性体物理发泡卷材的制备方法，包括以下步骤：
(1)将100份TPU颗粒(邵氏硬度为80A)、10份EVA颗粒和0.5份抗氧剂依次经干燥、预混合、双螺杆连续挤出、压延和收卷后，得厚度为0.3mm前驱热塑性弹性体卷材；
(2)将步骤(1)所得前驱热塑性弹性体卷材置入充满CO 2流体的高压容器中浸渍得到高压流体含量为9％的浸渍热塑性弹性体卷材，随后将浸渍热塑性弹性体卷材移入冷却腔采用液氮进行快速冷冻锁气处理，此时冷却腔内的温度为-10℃，再在-20℃下低温储存6h，低温储存6h后浸渍热塑性弹性体物理发泡卷材中高压流体的含量为6％，高压流体的质量失重率为33.3％；
(3)将低温储存的浸渍热塑性弹性体物理发泡卷材通入加热介质中并加热进行物理发泡后，经辊压、冷却、收卷后，即得所述热塑性弹性体物理发泡卷材。
经检测，与实施例2所得产品相比，所得热塑性弹性体物理发泡卷材的表面平整，厚度为1.3mm，长度为52m，密度为由0.3g/cm 3增加为0.6g/cm 3，芯层发泡泡孔平均尺寸约为85.6μm，邵氏硬度为45C。
最后所应当说明的是，以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。

Claims (10)

  1. 一种热塑性弹性体物理发泡卷材的半连续制备方法，其特征在于，包括以下步骤：
    (1)将热塑性弹性体和助剂依次经干燥、预混合、双螺杆连续挤出、压延和收卷后，得前驱热塑性弹性体卷材；
    (2)将步骤(1)所得前驱热塑性弹性体卷材置入高压流体中浸渍得到浸渍热塑性弹性体卷材，随后将浸渍热塑性弹性体卷材进行快速冷冻锁气处理并低温储存；所述浸渍热塑性弹性体卷材中高压流体的质量含量为1～15％；所述快速冷冻锁气处理的温度为-20～-100℃；所述低温储存的温度为-60～-20℃；所述浸渍时的高压流体包括CO 2流体、N 2流体中的至少一种；
    (3)将低温储存的浸渍热塑性弹性体卷材通入加热介质中并加热进行物理发泡后，经辊压、冷却、收卷后，即得所述热塑性弹性体物理发泡卷材；所述加热介质为热空气或热水。
  2. 如权利要求1所述热塑性弹性体物理发泡卷材的半连续制备方法，其特征在于，步骤(1)所述热塑性弹性体的邵氏硬度为60～95A，所述前驱热塑性弹性体卷材的厚度为0.1～3mm。
  3. 如权利要求1所述热塑性弹性体物理发泡卷材的半连续制备方法，其特征在于，步骤(1)所述热塑性弹性体包括TPU、TPEE、TPAE中的至少一种，所述助剂包括成核剂和抗氧剂。
  4. 如权利要求1所述热塑性弹性体物理发泡卷材的半连续制备方法，其特征在于，步骤(1)所述助剂还包括1～20份的气体阻隔剂；所述气体阻隔剂包括PVOH、PVA中的至少一种。
  5. 如权利要求1所述热塑性弹性体物理发泡卷材的半连续制备方法，其特征在于，步骤(1)所述前驱热塑性弹性体卷材还含有气体阻隔层，所述前驱热塑性弹性体卷材的制备方法为：将热塑性弹性体和助剂依次经干燥、预混合、双螺杆连续挤出、压延后，在弹性体表面涂覆含有PVA的水溶液，再经过干燥及收卷，得前驱热塑性弹性体卷材。
  6. 如权利要求5所述热塑性弹性体物理发泡卷材的半连续制备方法，其特征在于，所述气体阻隔层的厚度为0.01～0.05mm；所述PVA的水溶液中PVA的质量含量为5～30％。
  7. 如权利要求1所述热塑性弹性体物理发泡卷材的半连续制备方法，其特征在于，步骤(2)所述浸渍后得到的浸渍热塑性弹性体卷材中高压流体的质量含量为2～10％。
  8. 如权利要求1所述热塑性弹性体物理发泡卷材的半连续制备方法，其特征在于，步骤(2)所述快速冷冻锁气处理的温度为-50～-80℃。
  9. 如权利要求1～8任一项所述热塑性弹性体物理发泡卷材的半连续制备方法制备的热塑性 弹性体物理发泡卷材，其特征在于，所述热塑性弹性体物理发泡卷材在发泡前经过快速冷冻锁气及低温储存处理，所述热塑性弹性体物理发泡卷材的厚度为0.1～3mm，密度为0.1～0.6g/cm 3，发泡泡孔的尺寸为1～200μm，邵氏硬度为20～60C。
  10. 如权利要求9所述的热塑性弹性体物理发泡卷材，其特征在于，所述热塑性弹性体物理发泡卷材的厚度为0.5～2mm，所述热塑性弹性体物理发泡卷材包括不发泡皮层及其内部的发泡芯层，所述发泡芯层中发泡泡孔的尺寸为10～50μm。
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CN114410102B (zh) * 2022-01-29 2022-09-13 浙江环龙新材料科技有限公司 一种微孔热塑性聚氨酯纳米复合发泡卷材及其制备方法与在抛光垫中的应用
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