WO2021080518A1 - Composé de purge destinée au nettoyage d'une machine de traitement de plastique - Google Patents

Composé de purge destinée au nettoyage d'une machine de traitement de plastique Download PDF

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Publication number
WO2021080518A1
WO2021080518A1 PCT/TH2019/000049 TH2019000049W WO2021080518A1 WO 2021080518 A1 WO2021080518 A1 WO 2021080518A1 TH 2019000049 W TH2019000049 W TH 2019000049W WO 2021080518 A1 WO2021080518 A1 WO 2021080518A1
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WO
WIPO (PCT)
Prior art keywords
purging compound
cleaning
processing machine
plastic processing
purging
Prior art date
Application number
PCT/TH2019/000049
Other languages
English (en)
Inventor
Jirawut JUNKASEN
Navaporn KAERKITCHA
Supattra HEMMOOD
Narin KAABBUATHONG
Original Assignee
Ptt Public Company Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ptt Public Company Limited filed Critical Ptt Public Company Limited
Priority to PCT/TH2019/000049 priority Critical patent/WO2021080518A1/fr
Publication of WO2021080518A1 publication Critical patent/WO2021080518A1/fr

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Classifications

    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • 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
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/70—Maintenance
    • B29C33/72—Cleaning
    • B29C33/722—Compositions for cleaning moulds
    • 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
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • B29C45/1753—Cleaning or purging, e.g. of the injection unit
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/27—Cleaning; Purging; Avoiding contamination
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92009—Measured parameter
    • B29C2948/92209—Temperature
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • 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
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B29K2023/0608—PE, i.e. polyethylene characterised by its density
    • B29K2023/0633—LDPE, i.e. low density polyethylene
    • 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
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B29K2023/0608—PE, i.e. polyethylene characterised by its density
    • B29K2023/065—HDPE, i.e. high density polyethylene
    • 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
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B29K2023/0658—PE, i.e. polyethylene characterised by its molecular weight
    • B29K2023/0683—UHMWPE, i.e. ultra high molecular weight polyethylene
    • 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
    • B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
    • B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine

Definitions

  • the invention relates to the field of chemistry and polymer in relation to the development of purging compound for cleaning said plastic processing machine, e.g. plastic molding machine and mixing machine.
  • Recent developed purging compounds were categorized to three primary types.
  • the first type mechanical purging compound which is effective across a wide variety of applications, rely on shear force from the machine’s power and differences in material viscosities.
  • the mechanical type sometime consists of an abrasive material e.g. glass fiber, clay, calcium or talcum.
  • the second type chemical purging compound is a liquid or solid compound which can be effective in areas of low pressure where mechanical purges are sometime less effective, there is a chemical reaction occurs in the barrel or die to shorten the molecular chain of the residual resin, thus normally require soaking in the barrel for a specific period of time.
  • the last type hybrid purging compound which is the combination between mechanical and chemical purging compounds.
  • purging compounds are commercially available. This help the manufacturer to reduce the defects, e.g. black specks, minimize the time for cleaning screw and barrel, and no need the machine disassembly.
  • some purging compounds especially mechanical type purging compound, cause an aggressive scouring to the screw and barrel by abrasive fillers in the formulation.
  • Some purging compounds take long soaking time and may generate some smoke and/or odor from low molecular weight or thermally unstable components while using with high processing temperature which may be unsafe to an operator.
  • the manufacturer should select the appropriate purging compound to use with their process materials and types of machine; e.g. blow molding machine; injection molding; pipe, sheet, or profile extrusion machine.
  • the research and development of purging compound with higher efficiency, low smoke, odor free, and economical applications have been mentioned in several patent documents. Some examples are as follows:
  • U.S. patent application no. US20160101553A1 wherein the title of invention is “process for cleaning melt processing equipment”, discloses a process for cleaning melt processing equipment comprising at least 75 wt% of polyethylene having a viscosity number from 300 to 3,500 ml/g and an average particle size, d50, from 50 to 1000 micron, heating the melt processing equipment to a temperature sufficient to allow the purge material to be extruded through the equipment, and running the equipment to extrude the purge material while cleaning the melt processing equipment.
  • the research and development exist for a purging compound composition with no reaction that require time for soaking, low smoke and odor, and economical application in melt processing of plastic resin, while improve efficiency for cleaning impurities or any residuals in the screw and barrel.
  • the present invention relates to the development of purging compound for cleaning plastic processing machine wherein the purging compound comprising of virgin thermoplastic polymer and fluoropolymer component 0.1 -5.0% by weight of purging compound.
  • the virgin thermoplastic polymer is selected from low-density polyethylene, high-density polyethylene, ultrahigh molecular weight polymer, or combination thereof.
  • the ultrahigh molecular weight polymer in the present invention having a molecular weight from 1-10 Million g/mol.
  • the most preferred virgin thermoplastic polymer comprises of low- density polyethylene 55-76% by weight, high-density polyethylene 19-25% by weight, and ultrahigh molecular weight polymer 5-20% by weight of purging compound.
  • the objective of the invention is to develop purging compound that works well with low smoke and odor at the temperature range of 160-350 degree Celsius and can be used with the cleaning of various types of plastic resin, e.g. low-density polyethylene (LDPE), high-density polyethylene (HDPE), linear low-density polyethylene resin (LLDPE), polypropylene (PP), polyacrylonitrile-butadiene-styrene (ABS), polylactic acid (PLA) or polybutylene succinate (PBS) to clean industrial plastic processing machine that are chosen from extrusion machine, injection machine, or blow molding machine.
  • plastic resin e.g. low-density polyethylene (LDPE), high-density polyethylene (HDPE), linear low-density polyethylene resin (LLDPE), polypropylene (PP), polyacrylonitrile-butadiene-styrene (ABS), polylactic acid (PLA) or polybutylene succinate (PBS) to clean industrial plastic processing machine that are chosen from ex
  • the invention relates to the development of purging compound that works well with low smoke and odor at the temperature range of 160-350 degree Celsius to clean the plastic processing machine that are chosen from extrusion machine, injection machine, or blow molding machine.
  • the purging compound from the present invention can be used with the cleaning of various type of plastic resin, e.g. low-density polyethylene (LDPE), high-density polyethylene (HDPE), linear low-density polyethylene resin (LLDPE), polypropylene (PP), polyacrylonitrile-butadiene-styrene (ABS), polylactic acid (PLA) or polybutylene succinate (PBS).
  • LDPE low-density polyethylene
  • HDPE high-density polyethylene
  • LLDPE linear low-density polyethylene resin
  • PP polypropylene
  • ABS polyacrylonitrile-butadiene-styrene
  • PLA polylactic acid
  • PBS polybutylene succinate
  • the purging compound is comprising of virgin thermoplastic polymer and fluoropolymer component 0.1-5.0% by weight of purging compound, wherein said virgin thermoplastic polymer comprising of low-density polyethylene 55-76% by weight, high-density polyethylene 19-25% by weight, and ultrahigh molecular weight polymer 5- 20% by weight of purging compound.
  • the ultrahigh molecular weight polymer can be an ultrahigh molecular weight polyethylene (UHMWPE) in powder form which has high abrasion resistance and low coefficient of friction properties.
  • UHMWPE ultrahigh molecular weight polyethylene
  • An average molecular weight of UHMWPE can be chosen from 1-10 Million g/mol, for example from 3.2-6.0 Million g/mol.
  • the fluoropolymer can be a fluoro elastomer which is small molecule that can penetrate between impurity and screw or barrel resulting in better cleaning efficiency.
  • the suitable composition of the fluoropolymer used herein is 1.5-3.0% by weight of purging compound.
  • the mixture of LDP E and HDPE, and the mixture between powder of UHMWPE and fluoropolymer component are mixed using tumbler mixer before compounding for better mixing performance.
  • the purging compound is prepared by twin screw extruder wherein the plastic mixture of LDPE and HDPE is separatel fed via the main feeder, while the mixture between powder of UHMWPE and fluoropol mer component is fed via side feeder to allow more accurate quantit control of the elements.
  • inorganic filler can be comprised in the purging compound formulation for cost reduction purpose.
  • the inorganic filler is preferably chosen from magnesium carbonate (MgCCb), calcium carbonate (CaCC>3), talcum, calcium sulphate (CaSCfr), barium sulfate (BaSCL), silica, alumina, or nanoclay; and wherein the inorganic filler provides good efficienc for cleaning of plastic processing machine.
  • the suitable ratio of said inorganic filler is 0.1-10% by weight of purging compound.
  • the preferred size of inorganic filler is 2 micrometers, and the most preferred inorganic filler according to the present invention is calcium carbonate.
  • tais&v extruder used for preparation of the purging compound is specially set up to its best condition, i.e. extruder temperature of 80-230 degree Celsius, by increasing temperature of extruder from hopper to nozzle, and screw speed of 120 round per minutes (rpm) for good results.
  • the process for preparation of purging compound according to the present invention is done by following steps:
  • twin screw extruder i.e. extruder temperature of 80-230 degree Celsius, by increasing temperature of extruder from hopper to nozzle, and screw speed of 120 round per minutes (rpm).
  • Example 1 The preparation of different formula of purging compound with various mixing ratio.
  • the purging compounds with various mixing ratio are prepared by saidpreparationprocess according to one of preferred embodiment of the present invention to investigate the effect on cleaning efficiency of the plastic processing machine, i.e. injection molding machine.
  • the formula of purging compound with various mixing ratio are shown in table 1.
  • Example 1 Shows the formula of purging compound with various mixing ratio.
  • Example 2. The melt flow rate (MFR) of purging compound for cleaning plastic processing machine according to the present invention for various temperature.
  • melt flow rate MFR, g/10 min of the purging compound with various mixing ratio derived from Example 1 was determined by condition ASTM D-1238 for various temperature from 200-320 degree Celsius. The results are shown in figure 1.
  • the MFR of the purging compound is decrease with increasing composition of HOPE and UHMWPE.
  • an increasing amount of fluoropolymer component increases the MFR of the purging compound.
  • molecular weight of UHMWPE shows minor effect to the viscosity (or MFR) of the purging compound.
  • Efficiency evaluation of the purging compound with various mixing ratio derived from Example 1 is performed by cleaning of contaminate in an injection molding machine.
  • the mold is rectangular shape with 101.6 millimeters width x 152.4 millimeters length x 3.175 millimeters thickness.
  • the efficiency evaluation procedure by injection molding machine is as following steps:
  • Example 3 The efficiency evaluation of purging compound for cleaning plastic processing machine according to the present invention by using polypropylene (PP) as a simulant.
  • Efficiency evaluation of the purging compound with various mixing ratio derived from Example 1 for cleaning of PP simulant is performed by cleaning of mimicked contaminate PP, prepared by dry blend PP simulant 99% by weight with black masterbatch 1% by weight, by injection molding machine.
  • the injection temperature is set to 230 degree Celsius and injection speed is 50 rpm.
  • the efficiency evaluation is compared the total weight of purging material, which is sum of weight of purging compound (1 st PURGE) and weight of PP simulant (2 nd PURGE) used until a sample is perfect clean.
  • the efficiency of purging compound is compared to commercial pelletized purging compound. Test results are shown in table 2.
  • Table 2. Shows the MFR and weight of purging compound used to clean the mold of injection molding machine by using polypropylene (PP) as a simulant at 230 degree Celsius.
  • formula 8 that has inorganic filler content shows quite low efficiency for 2 nd purge due to the particles of inorganic filler were distributed in the simulant and difficult to clean from the mold of injection machine than other formula.
  • formula which blend with HOPE can clean the mold of injection molding machine with higher efficiency than the formula with LDPE alone, and the efficiency of cleaning is strongly depend on viscosity of the purging compound wherein the purging compound with higher viscosity (lower MFR) show higher cleaning efficiency (lower total weight of purging material) to clean the mold o f inj ection molding machine by using PP as a simulant.
  • Example 4 The efficiency evaluation of purging compound for cleaning plastic processing machine according to the present invention by using polyacrylonitrile-butadiene-styrene (ABS) as a simulant. Efficiency evaluation of the purging compound with various mixing ratio derived from ABS.
  • ABS polyacrylonitrile-butadiene-styrene
  • Example 1 for cleaning of ABS simulant is performed by cleaning of mimicked contaminate ABS, prepared by dry blend ABS simulant 99% by weight with black masterbatch 1% by weight, by injection molding machine.
  • the injection temperature is set to 320 degree Celsius and injection speed is 50 rpm.
  • the efficiency evaluation is compared the total weight of purging material, which is sum of weight of purging compound (1 st PURGE) and weight of ABS simulant (2 nd PURGE) used until a sample is perfect clean.
  • the efficiency of purging compound is compared to commercial pelletized purging compound. Test results are shown in table 3.
  • Table 3 Shows the MFR and weight of purging compound used to clean the mold of injection molding machine by using polyacrylonitrile-butadiene-styrene (ABS) as a simulant at 320 degree Celsius.
  • ABS polyacrylonitrile-butadiene-styrene
  • Example 5 The efficiency evaluation of purging compound for cleaning plastic processin machine according to the present invention by using polylactic acid (PLA) and polybutylene succinate (PBS) as a simulant.
  • PLA polylactic acid
  • PBS polybutylene succinate
  • PLA and PBS are use as representative simulants.
  • the purging compound formula 5, which has high efficiency regarding to the test results from Example 2 to 4, is applied for cleaning of mimicked contaminate PLA and PBS.
  • the mimicked contaminate prepares by dry blend simulant 99% by weight with black masterbatch 1% by weight.
  • the efficiency evaluation is performed by injection machine which injection temperature is set to 230 degree Celsius and injection speed is 50 rpm. Test results confirmed that the purging compound according to the present inven ion has high efficiency for cleaning various kind of simulant as shown in table 4.
  • Table 4. Shows the MFR and weight of purging compound used to clean the mold of injection molding machine by using various simulants.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Detergent Compositions (AREA)

Abstract

La divulgation concerne un composé de purge destinée au nettoyage d'une machine de traitement de plastique utilisée pour mélanger ou pour mouler une résine polymère présentant un bon fonctionnement et une faible fumée et une faible odeur à une plage de températures comprise entre 160 et 350 degrés Celsius. Le composé de purge est un polymère thermoplastique vierge comprenant un polymère à poids moléculaire ultra-élevé, présentant un poids moléculaire compris entre 1 et 10 millions g/mol, et un constituant fluoropolymère.
PCT/TH2019/000049 2019-10-22 2019-10-22 Composé de purge destinée au nettoyage d'une machine de traitement de plastique WO2021080518A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/TH2019/000049 WO2021080518A1 (fr) 2019-10-22 2019-10-22 Composé de purge destinée au nettoyage d'une machine de traitement de plastique

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/TH2019/000049 WO2021080518A1 (fr) 2019-10-22 2019-10-22 Composé de purge destinée au nettoyage d'une machine de traitement de plastique

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WO2021080518A1 true WO2021080518A1 (fr) 2021-04-29

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6022420A (en) 1997-03-04 2000-02-08 E. I. Du Pont De Nemours And Company Purging compound
JP4101596B2 (ja) * 2002-09-17 2008-06-18 旭化成ケミカルズ株式会社 優れた洗浄剤組成物
JP2009107160A (ja) * 2007-10-29 2009-05-21 Asahi Kasei Chemicals Corp 成形機用洗浄剤組成物
JP2013155211A (ja) * 2012-01-26 2013-08-15 Asahi Kasei Chemicals Corp 粒状洗浄剤、及びその製造方法、並びに成形機の洗浄方法
US20160101553A1 (en) 2014-10-10 2016-04-14 Ticona Llc Processes for cleaning melt processing equipment
CN109486566A (zh) * 2018-11-21 2019-03-19 赤途实业(上海)有限公司 一种高效螺杆清洗剂及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6022420A (en) 1997-03-04 2000-02-08 E. I. Du Pont De Nemours And Company Purging compound
JP4101596B2 (ja) * 2002-09-17 2008-06-18 旭化成ケミカルズ株式会社 優れた洗浄剤組成物
JP2009107160A (ja) * 2007-10-29 2009-05-21 Asahi Kasei Chemicals Corp 成形機用洗浄剤組成物
JP2013155211A (ja) * 2012-01-26 2013-08-15 Asahi Kasei Chemicals Corp 粒状洗浄剤、及びその製造方法、並びに成形機の洗浄方法
US20160101553A1 (en) 2014-10-10 2016-04-14 Ticona Llc Processes for cleaning melt processing equipment
CN109486566A (zh) * 2018-11-21 2019-03-19 赤途实业(上海)有限公司 一种高效螺杆清洗剂及其制备方法

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