CN106519283A - Polypropylene high-temperature supercritical foaming technology - Google Patents

Polypropylene high-temperature supercritical foaming technology Download PDF

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Publication number
CN106519283A
CN106519283A CN201610989168.9A CN201610989168A CN106519283A CN 106519283 A CN106519283 A CN 106519283A CN 201610989168 A CN201610989168 A CN 201610989168A CN 106519283 A CN106519283 A CN 106519283A
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China
Prior art keywords
polypropylene
temperature
calcium carbonate
caco
pressure
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CN201610989168.9A
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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 CN201610989168.9A priority Critical patent/CN106519283A/en
Publication of CN106519283A publication Critical patent/CN106519283A/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
    • C08J9/06—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
    • C08J9/12—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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • 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
    • C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams

Abstract

The invention discloses a polypropylene high-temperature supercritical foaming technology. The polypropylene high-temperature supercritical foaming technology comprises following steps: 1, uniformly mixed polypropylene PP and calcium carbonate CaCO3 are subjected to melt blending and extrusion so as to obtain polypropylene/calcium carbonate particles with a diameter of 2 to 4mm and a length of 2 to 5mm; 2, the polypropylene/calcium carbonate particles are delivered into a high pressure reactor, CO2 is injected into the high pressure reactor, the temperature in the high pressure reactor is increased to an infiltration temperature ranging from 170 to 180 DEG C, CO2 is injected into the high pressure reactor continuously until a saturation pressure ranging from 20 to 28MPa is reached, and the pressure is maintained for 20 to 50min; 3, the temperature is reduced to a foaming temperature ranging from 105 to 165 DEG C, the pressure is maintained to be constant in temperature increasing process, and the temperature is maintained for 40 to 90min; 4, the pressure is reduced to normal pressure in 10s, and an obtained foamed material is immersed in ice water mixture for shock cooling. Special technology is adopted, so that polypropylene is provided with a wider foaming temperature range, the conventional foaming temperature range of PP is increased by 14 times, from 4 DEG C to 60 DEG C, and technology extension is improved.

Description

A kind of polypropylene high-temperature supercritical foam process
Technical field
A kind of the present invention relates to automotive material technical field, more particularly to polypropylene high-temperature supercritical foam process.
Background technology
Polymeric foamable material is referred to based on polymer and its internal material with countless abscesses, it is also possible to be considered as Composite with gas as filler.Which 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, insulant, 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, and 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 Cause serious " white pollution " afterwards to environment, can give off poisonous gas during burning；PS and PE expanded material heat resistances are poor, Obvious thermal deformation can occur when 105 DEG C, be not suitable for using at a higher temperature.Therefore, their application receives very big Limit.
Since 20 century 70s, as the third-largest general-purpose plastics polypropylene for being only second to PE and polrvinyl 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, the degradable under natural environment.
Using its excellent thermostability, 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 the trend with other expanded materials of replacement.Therefore, in recent years Come many countries and greatly develop PP expanded materials, but, as 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 high-temperature supercritical foam 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 is employed the following technical solutions：
A kind of polypropylene high-temperature supercritical foam process, including：
(1) by the polypropylene PP of mix homogeneously and Calcium Carbonate CaCO3Melt blending is extruded, and obtains a diameter of 2-4mm, length Polypropylene/the calcium carbonate granule of 2-5mm；
(2) autoclave is terminated in by polypropylene/calcium carbonate granule anti-, be filled with CO2, it is warming up to infiltration temperature 170-180 DEG C, continue to be filled with CO2To saturation pressure 20-28MPa, and pressurize 20-50min；
(3) high-temperature is dropped to 105-165 DEG C of blowing temperature, keep pressure constant, be incubated 40-90min in temperature-rise period；
(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 are as follows：
(1) by n-CaCO3Drying, the moisture on surface of going out；
(2) by the n-CaCO of dry tack free3Dehydrated alcohol is scattered in, and addition accounts for CaCO3Quality 1-5% it is silane coupled Agent, and stir；
(3) centrifugation wash CaCO3, 36-60 hours are dried at 55-65 DEG C, 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。
The blowing temperature of high temperature dipping foaming is interval big compared with traditional foaming, up to 15 times of tradition foaming, and this is Determined by high melt temperature and low crystallization temperature.PP/n-CaCO3The interval purer PP of blowing temperature it is little, be primarily due to n-CaCO3Addition will not cause the change of PP melt temperatures, but, the gentle non-isothermal crystallizing process such as can accelerate, improve and send out The lower limit temperature of bubble temperature range, therefore, blowing temperature is interval to be reduced.
With the rising of blowing temperature, the abscess aperture increases of PP expanded materials, cell density reduce：With the increasing of saturation pressure Plus, the abscess aperture of PP expanded materials reduces, and cell density is big：n-CaCO3Addition can be obviously improved the foaminess of PP Can, obtain the expanded material of abscess fine uniform, but n-CaCO3Cell size size heterogeneity can be caused excessively.Work as foaming When temperature is raised, it is that gas diffusion determines foam structure first, continues to raise blowing temperature, the merger of abscess gradually occupies master Lead.
The present invention adopts specific technique so that polypropylene has broader blowing temperature interval, blowing temperature it is interval by Traditional PP blowing temperatures are interval only 4 DEG C, increased 60 DEG C, increased 15 times, increased its process spread.
Specific embodiment
Technical scheme is further illustrated below by specific embodiment.
Embodiment 1
A kind of polypropylene high-temperature supercritical foam process, including：
(1) by the polypropylene PP of mix homogeneously and Calcium Carbonate CaCO3Melt blending is extruded, and obtains a diameter of 4mm, length Polypropylene/the calcium carbonate granule of 2mm；
(2) autoclave is terminated in by polypropylene/calcium carbonate granule anti-, be filled with CO2, 180 DEG C of infiltration temperature is warming up to, after It is continuous to be filled with CO2To saturation pressure 25MPa, and pressurize 30min；
(3) 105 DEG C of blowing temperature is warming up to, is kept pressure constant in temperature-rise period, is incubated 90min；
(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 high-temperature supercritical foam process, including：
(1) by the polypropylene PP of mix homogeneously and Calcium Carbonate CaCO3Melt blending is extruded, and obtains a diameter of 2mm, length Polypropylene/the calcium carbonate granule of 5mm；
(2) autoclave is terminated in by polypropylene/calcium carbonate granule anti-, be filled with CO2, 170 DEG C of infiltration temperature is warming up to, after It is continuous to be filled with CO2To saturation pressure 25MPa, and pressurize 20min；
(3) 152 DEG C of blowing temperature is warming up to, is kept pressure constant in temperature-rise period, is incubated 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.
Embodiment 3
A kind of polypropylene high-temperature supercritical foam process, including：
(1) by the polypropylene PP of mix homogeneously and Calcium Carbonate CaCO3Melt blending is extruded, and obtains a diameter of 2-4mm, length Polypropylene/the calcium carbonate granule of 2-5mm；
(2) autoclave is terminated in by polypropylene/calcium carbonate granule anti-, be filled with CO2, 175 DEG C of infiltration temperature is warming up to, after It is continuous to be filled with CO2To saturation pressure 22MPa, and pressurize 50min；
(3) 165 DEG C of blowing temperature is warming up to, is kept pressure constant in temperature-rise period, is incubated 60min；
(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 high-temperature supercritical foam process, including：
(1) by the polypropylene PP of mix homogeneously and Calcium Carbonate CaCO3Melt blending is extruded, and obtains a diameter of 2-4mm, length 2-5mm Polypropylene/calcium carbonate granule；
(2) autoclave is terminated in by polypropylene/calcium carbonate granule anti-, be filled with CO2, 170-180 DEG C of infiltration temperature is warming up to, after It is continuous to be filled with CO2To saturation pressure 20-28MPa, and pressurize 20-50min；
(3) high-temperature is dropped to 105-165 DEG C of blowing temperature, keep pressure constant, be incubated 40-90min in temperature-rise period；
(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 high-temperature supercritical foam 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 high-temperature supercritical foam 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 free3Dehydrated alcohol is scattered in, and addition accounts for CaCO3The silane coupler of quality 1-5%, and Stir；
(3) centrifugation wash CaCO3, 36-60 hours are dried at 55-65 DEG C, obtain the modified n-CaCO in surface3。
4. polypropylene high-temperature supercritical foam process as claimed in claim 1, it is characterised in that the polypropylene/Calcium Carbonate In granule, polypropylene:Calcium Carbonate mass ratio is 97:3～90:10, preferably 97:3～95:5.
CN201610989168.9A 2016-11-10 2016-11-10 Polypropylene high-temperature supercritical foaming technology Pending CN106519283A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107619496A (en) * 2017-07-05 2018-01-23 四川大学 Foamable polymer composite of bimodal hole-closing structure and preparation method thereof
CN109591344A (en) * 2018-12-18 2019-04-09 晋江国盛新材料科技有限公司 A kind of moulding process of surface skining foaming air bag body
CN112002800A (en) * 2020-09-02 2020-11-27 哈尔滨工程大学 Preparation method of composite piezoelectric electret material
WO2020259125A1 (en) * 2019-06-27 2020-12-30 华东理工大学 Polypropylene material foaming method using supercritical fluid

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研究机理", 《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
CN107619496A (en) * 2017-07-05 2018-01-23 四川大学 Foamable polymer composite of bimodal hole-closing structure and preparation method thereof
CN107619496B (en) * 2017-07-05 2020-09-15 四川大学 Foamed polymer composite material with bimodal closed-cell structure and preparation method thereof
CN109591344A (en) * 2018-12-18 2019-04-09 晋江国盛新材料科技有限公司 A kind of moulding process of surface skining foaming air bag body
WO2020259125A1 (en) * 2019-06-27 2020-12-30 华东理工大学 Polypropylene material foaming method using supercritical fluid
CN112002800A (en) * 2020-09-02 2020-11-27 哈尔滨工程大学 Preparation method of composite piezoelectric electret material

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