CN106750485A - A kind of polypropylene low temperature supercritical foaming process - Google Patents

A kind of polypropylene low temperature supercritical foaming process Download PDF

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Publication number
CN106750485A
CN106750485A CN201610989169.3A CN201610989169A CN106750485A CN 106750485 A CN106750485 A CN 106750485A CN 201610989169 A CN201610989169 A CN 201610989169A CN 106750485 A CN106750485 A CN 106750485A
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China
Prior art keywords
polypropylene
calcium carbonate
caco
low temperature
foaming process
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Pending
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CN201610989169.3A
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Chinese (zh)
Inventor
张达明
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Wuxi Mingsheng Strong Blower Co Ltd
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Wuxi Mingsheng Strong Blower Co Ltd
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Priority to CN201610989169.3A priority Critical patent/CN106750485A/en
Publication of CN106750485A publication Critical patent/CN106750485A/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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/06—CO2, N2 or noble gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/08—Supercritical fluid
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—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
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The invention discloses a kind of polypropylene low temperature supercritical foaming process, including：(1) by well mixed polypropylene PP and calcium carbonate CaCO3Melt blending is extruded, and obtains a diameter of 2 4mm, the polypropylene/calcium carbonate granule of the 5mm of length 2；(2) polypropylene/calcium carbonate granule is prevented terminating in autoclave, is filled with CO2, 40 80 DEG C of infiltration temperature is warming up to, continue to be filled with CO2To the 28MPa of saturation pressure 20, and pressurize 16 48 hours；(3) 150 160 DEG C of blowing temperature is warming up to, keeps pressure constant in temperature-rise period, be incubated 10 40min；(4) pressure release, to normal pressure, foamed is taken out and is placed into chilling in mixture of ice and water in 10 seconds.The present invention uses specific technique so that polypropylene has broader blowing temperature interval, increased its process spread.

Description

A kind of polypropylene low temperature supercritical foaming process
Technical field
The present invention relates to automotive material technical field, more particularly to a kind of polypropylene low temperature supercritical foaming process.
Background technology
Polymeric foamable material refers to based on polymer and its internal material with countless abscesses, it is also possible to be considered as Composite with gas as filler.It has the features such as density is low, heat insulation performance is good, specific strength is high.It is daily in family The industries such as product, the vehicles, insulating materials, packaging material, fire proofing, electrical equipment, sports facility, electronic product extensively should With.High performance expanded material then plays a significant role in leading-edge fields such as military affairs, Aero-Space.
Polymeric foamable material is various in style, wherein most widely used is polystyrene (PS) and polyethylene (PE) foaming Material.But, there are many defects in PS and PE expanded materials, such as PS expanded materials are difficult degraded under natural environment, discard Serious " white pollution " is caused to environment afterwards, can be given off poisonous gas during burning；PS and PE expanded material heat resistances are poor, Obvious thermal deformation can occur at 105 DEG C, be not suitable for using at a higher temperature.Therefore, their application receives very big Limitation.
Since 20 century 70s, as the third-largest general-purpose plastics polypropylene for being only second to PE and polyvinyl chloride (PVC) (PP) progressed into foaming researcher the visual field, PP expanded materials not only have many excellent performances, and it is recyclable again Utilize, it is degradable under natural environment.
Using its excellent heat resistance, wholesomeness, thermal insulation and good environmental effect, PP expanded materials can be in bag The fields such as dress, automobile, insulation, building play a significant role, and with the trend of other expanded materials of substitution.Therefore, in recent years Come many countries and greatly develop PP expanded materials, but, because PP is a kind of semicrystalline polymeric, the humidity province that can be foamed Between (be referred to as blowing temperature interval) it is narrow, only 4 DEG C, foaming difficulty is big.
The content of the invention
It is an object of the invention to propose a kind of polypropylene low temperature supercritical foaming process, change conventional polypropylene foaming In, polypropylene expanded ability, the unmanageable defect of foam structure.
It is that, up to this purpose, the present invention uses following technical scheme：
A kind of polypropylene low temperature supercritical foaming process, including：
(1) by well mixed polypropylene PP and calcium carbonate CaCO3Melt blending is extruded, and obtains a diameter of 2-4mm, length Polypropylene/the calcium carbonate granule of 2-5mm；
(2) polypropylene/calcium carbonate granule is prevented terminating in autoclave, is filled with CO2, 40-80 DEG C of infiltration temperature is warming up to, Continue to be filled with CO2To saturation pressure 20-28MPa, and pressurize 16-48 hours；
(3) 150-160 DEG C of blowing temperature is warming up to, keeps pressure constant in temperature-rise period, be incubated 10-40min；
(4) pressure release, to normal pressure, foamed is taken out and is placed into chilling in mixture of ice and water in 10 seconds.
Preferably, the calcium carbonate is the n-CaCO that silane coupler surface is modified3, it is this area that the surface is modified Already known processes, its typical but non-limiting example is as follows：
(1) by n-CaCO3Drying, the moisture on surface of going out；
(2) by the n-CaCO of dry tack free3Absolute ethyl alcohol is scattered in, and addition accounts for CaCO3Quality 1-5%'s is silane coupled Agent, and stir；
(3) centrifugation and CaCO is washed3, dried at 55-65 DEG C 36-60 hours, obtain the modified n-CaCO in surface3。
In the polypropylene/calcium carbonate granule, polypropylene:Calcium carbonate mass ratio is 97:3~90:10, preferably 97:3~ 95:5。n-CaCO3With bigger serface, heterogeneous nucleation can be played a part of in foaming process, be managed according to classical nucleation By the nucleation free energy needed for heterogeneous nucleation is small, and cell nucleation easily, works as n-CaCO3When increasing containing two, heterogeneous nucleation point increases Many, nucleation amount increases, cell density increase, and abscess aperture reduces under same volume.But, work as n-CaCO3After content is excessive, n- CaCO3Sent out in PP and reunited, heterogeneous nucleation point is reduced, cell density reduces, abscess aperture increases.
With the increase of saturation pressure, the change of expanded material abscess aperture and cell density is different, PP expanded materials Abscess aperture first increases and then decreases, when saturation pressure is 22MPa, abscess aperture reaches maximum, about 37.3 μm, and steeps Hole density gradually increases with the increase of saturation pressure；When saturation pressure is less than 22MPa, the abscess aperture of expanded material and abscess Density increases rapidly, and when saturation pressure is higher than 22MPa, abscess aperture and cell density are constant.
Influence of the saturation pressure to expansion ratio is maximum, next to that the influence of blowing temperature, is again the shadow of infiltrating time Ring, the influence of foamed time is minimum.Influence of the blowing temperature to abscess aperture is maximum, next to that the influence of saturation pressure, again It is the influence of infiltration temperature, the influence of foamed time is minimum.When blowing temperature is 152 DEG C, saturation pressure is 28MPa, infiltration temperature It is 40 DEG C to spend, and when foamed time is 30min, the abscess aperture of expanded material is minimum, and cell density is maximum.
The present invention uses specific technique so that polypropylene has broader blowing temperature interval, increased the expansion of its technique Exhibition.
Specific embodiment
Technical scheme is further illustrated below by specific embodiment.
Embodiment 1
A kind of polypropylene low temperature supercritical foaming process, including：
(1) by well mixed polypropylene PP and calcium carbonate CaCO3Melt blending is extruded, and obtains a diameter of 4mm, length Polypropylene/the calcium carbonate granule of 2mm；
(2) polypropylene/calcium carbonate granule is prevented terminating in autoclave, is filled with CO2, 80 DEG C of infiltration temperature is warming up to, after It is continuous to be filled with CO2To saturation pressure 25MPa, and pressurize 24 hours；
(3) 154 DEG C of blowing temperature is warming up to, keeps pressure constant in temperature-rise period, be incubated 30min；
(4) pressure release, to normal pressure, foamed is taken out and is placed into chilling in mixture of ice and water in 10 seconds.
Embodiment 2
A kind of polypropylene low temperature supercritical foaming process, including：
(1) by well mixed polypropylene PP and calcium carbonate CaCO3Melt blending is extruded, and obtains a diameter of 2mm, length Polypropylene/the calcium carbonate granule of 5mm；
(2) polypropylene/calcium carbonate granule is prevented terminating in autoclave, is filled with CO2, 60 DEG C of infiltration temperature is warming up to, after It is continuous to be filled with CO2To saturation pressure 25MPa, and pressurize 16 hours；
(3) 152 DEG C of blowing temperature is warming up to, keeps pressure constant in temperature-rise period, be incubated 140min；
(4) pressure release, to normal pressure, foamed is taken out and is placed into chilling in mixture of ice and water in 10 seconds.
Embodiment 3
A kind of polypropylene low temperature supercritical foaming process, including：
(1) by well mixed polypropylene PP and calcium carbonate CaCO3Melt blending is extruded, and obtains a diameter of 2-4mm, length Polypropylene/the calcium carbonate granule of 2-5mm；
(2) polypropylene/calcium carbonate granule is prevented terminating in autoclave, is filled with CO2, 80 DEG C of infiltration temperature is warming up to, after It is continuous to be filled with CO2To saturation pressure 22MPa, and pressurize 48 hours；
(3) 154 DEG C of blowing temperature is warming up to, keeps pressure constant in temperature-rise period, be incubated 104min；
(4) pressure release, to normal pressure, foamed is taken out and is placed into chilling in mixture of ice and water in 10 seconds.
Embodiment 1-3 proves that the method for the present invention has broader blowing temperature interval.

Claims (4)

1. a kind of polypropylene low temperature supercritical foaming process, including：
(1) by well mixed polypropylene PP and calcium carbonate CaCO3Melt blending is extruded, and obtains a diameter of 2-4mm, length 2-5mm Polypropylene/calcium carbonate granule；
(2) polypropylene/calcium carbonate granule is prevented terminating in autoclave, is filled with CO2, 40-80 DEG C of infiltration temperature is warming up to, continue It is filled with CO2To saturation pressure 20-28MPa, and pressurize 16-48 hours；
(3) 150-160 DEG C of blowing temperature is warming up to, keeps pressure constant in temperature-rise period, be incubated 10-40min；
(4) pressure release, to normal pressure, foamed is taken out and is placed into chilling in mixture of ice and water in 10 seconds.
2. polypropylene low temperature supercritical foaming process as claimed in claim 1, it is characterised in that the calcium carbonate is silane idol The modified n-CaCO in connection agent surface3。
3. polypropylene low temperature supercritical foaming process as claimed in claim 2, it is characterised in that the surface modification technology is such as Under：
(1) by n-CaCO3Drying, the moisture on surface of going out；
(2) by the n-CaCO of dry tack free3Absolute ethyl alcohol is scattered in, and addition accounts for CaCO3The silane coupler of quality 1-5%, and Stir；
(3) centrifugation and CaCO is washed3, dried at 55-65 DEG C 36-60 hours, obtain the modified n-CaCO in surface3。
4. polypropylene low temperature supercritical foaming process as claimed in claim 1, it is characterised in that the polypropylene/calcium carbonate In particle, polypropylene:Calcium carbonate mass ratio is 97:3~90:10, preferably 97:3~95:5.
CN201610989169.3A 2016-11-10 2016-11-10 A kind of polypropylene low temperature supercritical foaming process Pending CN106750485A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107629241A (en) * 2017-10-19 2018-01-26 宁波致微新材料科技有限公司 A kind of preparation method of microporous foam polypropylene reflectance coating
CN107778516A (en) * 2017-10-19 2018-03-09 宁波致微新材料科技有限公司 A kind of preparation method of polymer micro expanded material
CN110713391A (en) * 2019-10-11 2020-01-21 成都新柯力化工科技有限公司 Light cement insulation board for energy-saving building and preparation method
CN111205504A (en) * 2020-03-19 2020-05-29 福建鑫瑞新材料科技有限公司 Thermoplastic elastomer bead foam and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
丁杰: "聚丙烯超临界二氧化碳发泡成型及机理研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107629241A (en) * 2017-10-19 2018-01-26 宁波致微新材料科技有限公司 A kind of preparation method of microporous foam polypropylene reflectance coating
CN107778516A (en) * 2017-10-19 2018-03-09 宁波致微新材料科技有限公司 A kind of preparation method of polymer micro expanded material
CN110713391A (en) * 2019-10-11 2020-01-21 成都新柯力化工科技有限公司 Light cement insulation board for energy-saving building and preparation method
CN111205504A (en) * 2020-03-19 2020-05-29 福建鑫瑞新材料科技有限公司 Thermoplastic elastomer bead foam and preparation method thereof
CN111205504B (en) * 2020-03-19 2022-09-06 福建鑫瑞新材料科技有限公司 Thermoplastic elastomer bead foam and preparation method thereof

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