CN107226989A - A kind of acrylic resin that hollow product is prepared suitable for blow molding process - Google Patents
A kind of acrylic resin that hollow product is prepared suitable for blow molding process Download PDFInfo
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- CN107226989A CN107226989A CN201610168595.0A CN201610168595A CN107226989A CN 107226989 A CN107226989 A CN 107226989A CN 201610168595 A CN201610168595 A CN 201610168595A CN 107226989 A CN107226989 A CN 107226989A
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- Prior art keywords
- acrylic resin
- molding process
- blow molding
- hollow product
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- 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
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
Abstract
The present invention relates to a kind of acrylic resin that hollow product is prepared suitable for blow molding process, after acrylic resin base-material is well mixed with composite assistant, it is added in double screw extruder and carries out melt pelletization, produce.The acrylic resin base-material is the block copolymer of propylene and ethene, and ethylene contents are 4 7wt%, and melt flow rate (MFR) is 0.1 5.0g/10min.The composite assistant includes halogen-absorber and antioxidant.The acrylic resin of the present invention has higher melt strength and preferable melt ductility simultaneously, hollow product can be prepared by extrusion-blown modling equipment, it is uniform using the product wall thickness of the acrylic resin extrusion-blown modling, while also maintaining intensity, the heat-resisting and chemical reagent-resistant performance that polypropylene should have.
Description
Technical field
The present invention relates to a kind of acrylic resin, particularly a kind of polypropylene tree that hollow product is prepared suitable for blow molding process
Fat.
Background content
Polyethylene (PE) is the earliest kind for realizing merchandized handling in plastics blow moulding moulding material, is also to develop most
Hurry up, most widely used kind, at present, the yield of the Blow Molded Articles produced by raw material of PE accounts for world's blow-molded article
Total output about 2/3rds, wherein, middle-size and small-size hollow product is larger to the demand of polyethylene, accounts for 80%.It is common poly-
The melt strength of propylene (PP) is relatively low, and sag resistant poor-performing in blow-molding process, therefore applied to hollow product side
The research in face is seldom, however, PP has mechanical performance more more preferable than PE and rigidity, and polyacrylic heat resistance in itself
It is better than polyethylene, when polypropylene is applied to hollow product, compared to PE products, both cost can be reduced with material saving,
And resulting product intensity itself and heat resistance are more excellent.Therefore, research and development are special suitable for the PP of hollow product
Material is with certain potential market value and prospect.
The content of the invention
The sag resistant performance present invention aim to address plain polypropylene resin melt strength in the prior art is low, in blow-molding process
Poor the problem of, makes it be applied to blow while have the acrylic resin of high fondant-strength and high melt ductility there is provided a kind of
Modeling technique prepares hollow product.
The present inventor carries out specific aim adjustment by the molecular weight to acrylic resin base-material, while improving polypropylene tree
The melt strength and melt ductility of fat, and the extrusion temperature and extruded velocity of selection resin are further advanced by, so as to solve
Technological deficiency during hollow polypropylene product is prepared using blow molding process in the prior art.
Technical scheme
A kind of acrylic resin that hollow product is prepared suitable for blow molding process, is prepared from by the following method：By polypropylene tree
After aliphatic radical material is well mixed with composite assistant, it is added in double screw extruder and carries out melt pelletization, produce.
The acrylic resin base-material is the block copolymer of propylene and ethene, and ethylene contents are 4-7wt%, melt flows speed
Rate is 0.1-5.0g/10min, most preferably 0.4-0.8g/10min.
The composite assistant includes halogen-absorber and antioxidant, and the dosage of halogen-absorber is acrylic resin base-material
0.02-0.3wt%, the dosage of antioxidant is the 0.04-0.5wt% of acrylic resin base-material.
Further, the halogen-absorber is any one in calcium stearate or hydrotalcite.
Further, the antioxidant is two-[3,3- bis--(3- tert-butyl-hydroxy phenyls)-butyric acid] glycol esters, four [β-(3,5-
Di-tert-butyl-hydroxy phenyl) propionic acid] one or both of pentaerythritol ester or three (2,3- di-tert-butyl-phenyls) phosphite esters
The mixture of any of the above ratio.Preferably four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters and three (2,3-
Di-tert-butyl-phenyl) phosphite ester mixture.
Further, the draw ratio of the double screw extruder is 40, and screw speed is 100-300r/min.
Further, each area's temperature of the double screw extruder is respectively：One 130-135 DEG C of area, two 150-170 DEG C of areas,
Three 180-200 DEG C of areas, four 190-210 DEG C of areas, five 190-210 DEG C of areas, six 190-210 DEG C of areas, seven 190-210 DEG C of areas, eight
190-210 DEG C of area.
In above-mentioned technique, the block copolymer of propylene and ethene uses method well known in the art and is prepared into what is come, for example
BP-Amoco polymarization method for prodcing polyacrylates.
Above-mentioned acrylic resin has higher melt strength and preferable melt ductility simultaneously, is set by extrusion-blown modling
It is standby, under certain extrusion temperature and rate of extrusion, hollow product can be prepared.Prepared by technical solution of the present invention
The product wall thickness of obtained acrylic resin extrusion-blown modling is uniform, at the same also maintain intensity that polypropylene should have, it is heat-resisting
And chemical reagent-resistant performance.
Embodiment
Explanation：For the ease of comparing, what the preparation method of the block copolymer of propylene and ethene in following embodiments was used
It is BP-Amoco polymarization method for prodcing polyacrylates.
Embodiment 1
By the block copolymerization that 100 parts of ethylene contents are propylene and ethene that 6wt%, melt flow rate (MFR) are 0.6g/10min
Thing and 0.1 part of calcium stearate, the four of 0.2 part [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters and 0.1
Three (2,3- di-tert-butyl-phenyl) phosphite esters of part uniformly after mixing, are added in double screw extruder and carry out melt pelletization,
Produce.The draw ratio of double screw extruder is 40, and screw speed is 200r/min, and each area's temperature of double screw extruder is：
One 130 DEG C of area, two 160 DEG C of areas, three 190 DEG C of areas, four 200 DEG C of areas, five 200 DEG C of areas, six 205 DEG C of areas, seven 210 DEG C of areas,
Eight 210 DEG C of areas.
Embodiment 2
The ethylene contents of the block copolymer of propylene and ethene are that 6wt%, melt flow rate (MFR) are 0.8g/10min, twin-screw
Each area's temperature of extruder is：One 135 DEG C of area, two 165 DEG C of areas, three 185 DEG C of areas, four 190 DEG C of areas, five 190 DEG C of areas,
Six 195 DEG C of areas, seven 200 DEG C of areas, eight 205 DEG C of areas, remaining is same as Example 1.
Embodiment 3
By the block copolymerization that 100 parts of ethylene contents are propylene and ethene that 6wt%, melt flow rate (MFR) are 0.6g/10min
Thing and 0.1 part of hydrotalcite, 0.2 part of four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and 0.1 part
Three (2,3- di-tert-butyl-phenyl) phosphite esters carry out twin-screw melt pelletization, remaining technological parameter and embodiment 1 after uniformly mixing
It is identical.
Embodiment 4
By the block copolymerization that 100 parts of ethylene contents are propylene and ethene that 6wt%, melt flow rate (MFR) are 0.6g/10min
Thing and 0.05 part of calcium stearate, 0.2 part four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and 0.1
Three (2,3- di-tert-butyl-phenyl) phosphite esters of part carry out twin-screw melt pelletization, remaining technological parameter and reality after uniformly mixing
Apply example 1 identical.
Embodiment 5
By the block copolymerization that 100 parts of ethylene contents are propylene and ethene that 6wt%, melt flow rate (MFR) are 0.6g/10min
Thing and 0.3 part of calcium stearate, 0.2 part four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and 0.1
Three (2,3- di-tert-butyl-phenyl) phosphite esters of part carry out twin-screw melt pelletization, remaining technological parameter and reality after uniformly mixing
Apply example 1 identical.
Embodiment 6
By the block copolymerization that 100 parts of ethylene contents are propylene and ethene that 6wt%, melt flow rate (MFR) are 0.6g/10min
Thing and 0.1 part of calcium stearate, 0.2 part of two-[3,3- bis--(3- tert-butyl-hydroxy phenyls)-butyric acid] glycol esters and 0.1
Part three (2,3- di-tert-butyl-phenyl) phosphite esters uniformly carry out twin-screw melt pelletization, remaining and the phase of embodiment 1 after mixing
Together.
Embodiment 7
By the block copolymerization that 100 parts of ethylene contents are propylene and ethene that 6wt%, melt flow rate (MFR) are 0.6g/10min
Thing and 0.1 part of calcium stearate, 0.1 part four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and 0.1
Three (2,3- di-tert-butyl-phenyl) phosphite esters of part carry out twin-screw melt pelletization, remaining technological parameter and reality after uniformly mixing
Apply example 1 identical.
Performance test
Acrylic resin made from embodiment 1-7 is subjected to melt strength, melt ductility and conventional mechanical property test,
And acrylic resin made from each embodiment is subjected to extrusion bottle blowing, the extrusion temperature of extrusion equipment by extrusion-blown modling equipment respectively
Spend for 190 DEG C, rate of extrusion is 0.6m/min, test result see the table below：
Claims (7)
1. a kind of prepare the acrylic resin of hollow product suitable for blow molding process, it is characterised in that prepare by the following method and
Into：After acrylic resin base-material is well mixed with composite assistant, it is added in double screw extruder and carries out melt pelletization, i.e.,
；
The acrylic resin base-material is the block copolymer of propylene and ethene, and ethylene contents are 4-7wt%, melt flows speed
Rate is 0.1-5.0g/10min；
The composite assistant includes halogen-absorber and antioxidant, and the dosage of halogen-absorber is acrylic resin base-material
0.02-0.3wt%, the dosage of antioxidant is the 0.04-0.5wt% of acrylic resin base-material.
2. the acrylic resin of hollow product is prepared suitable for blow molding process as claimed in claim 1, it is characterised in that institute
The melt flow rate (MFR) for stating the block copolymer of propylene and ethene is 0.4-0.8g/10min.
3. the acrylic resin of hollow product is prepared suitable for blow molding process as claimed in claim 1, it is characterised in that
The halogen-absorber is any one in calcium stearate or hydrotalcite.
4. the acrylic resin of hollow product is prepared suitable for blow molding process as claimed in claim 1, it is characterised in that
The antioxidant is two-[3,3- bis--(3- tert-butyl-hydroxy phenyls)-butyric acid] glycol esters, four [β-(3,5- di-t-butyl -4- hydroxyls
Base phenyl) propionic acid] one or both of pentaerythritol ester or three (2,3- di-tert-butyl-phenyls) phosphite esters any of the above ratio
Mixture.
5. the acrylic resin of hollow product is prepared suitable for blow molding process as claimed in claim 4, it is characterised in that
The antioxidant is that four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters and three (2,3- di-tert-butyl-phenyls) are sub-
The mixture of phosphate.
6. the acrylic resin of hollow product is prepared suitable for blow molding process as claimed in claim 1, it is characterised in that
The draw ratio of the double screw extruder is 40, and screw speed is 100-300r/min.
7. it is applied to the acrylic resin that blow molding process prepares hollow product as described in any one of claim 1 to 6, its
It is characterised by, each area's temperature of the double screw extruder is respectively：One 130-135 DEG C of area, two 150-170 DEG C of areas, three
180-200 DEG C of area, four 190-210 DEG C of areas, five 190-210 DEG C of areas, six 190-210 DEG C of areas, seven 190-210 DEG C of areas, 8th area
190-210℃。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610168595.0A CN107226989A (en) | 2016-03-23 | 2016-03-23 | A kind of acrylic resin that hollow product is prepared suitable for blow molding process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610168595.0A CN107226989A (en) | 2016-03-23 | 2016-03-23 | A kind of acrylic resin that hollow product is prepared suitable for blow molding process |
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| Publication Number | Publication Date |
|---|---|
| CN107226989A true CN107226989A (en) | 2017-10-03 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610168595.0A Pending CN107226989A (en) | 2016-03-23 | 2016-03-23 | A kind of acrylic resin that hollow product is prepared suitable for blow molding process |
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| CN (1) | CN107226989A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107880402A (en) * | 2017-11-23 | 2018-04-06 | 上海帆顺包装集团有限公司 | It is adapted to the high transparency high impact resistance polypropylene resin of blow molding process |
| CN107915900A (en) * | 2017-11-23 | 2018-04-17 | 上海帆顺包装集团有限公司 | A kind of suitable blow molding process prepares the acrylic resin of clear hollow product |
| CN108219291A (en) * | 2018-01-09 | 2018-06-29 | 上海帆顺包装集团有限公司 | A kind of acrylic resin and preparation method that hollow product is prepared suitable for blow molding process |
| CN109467824A (en) * | 2018-10-09 | 2019-03-15 | 中国石油化工股份有限公司 | A kind of polypropylene for films composition and preparation method thereof |
| CN115536945A (en) * | 2022-11-03 | 2022-12-30 | 北方华锦化学工业股份有限公司 | Low-melting-index transparent polypropylene resin for blow molding and preparation method thereof |
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|---|---|---|---|---|
| CN101724203A (en) * | 2008-10-31 | 2010-06-09 | 中国石化上海石油化工股份有限公司 | Polypropylene resin suitable for manufacturing medical infusion bottle by using injection stretch blow moulding process |
| CN102391585A (en) * | 2011-10-08 | 2012-03-28 | 中国石油化工股份有限公司 | Polypropylene material for transparent bottles and preparation method thereof |
| CN102532727A (en) * | 2011-12-19 | 2012-07-04 | 江苏金发科技新材料有限公司 | Blow molding grade halogen-free flame-retardant polypropylene material and preparation method thereof |
| CN103073798A (en) * | 2011-10-25 | 2013-05-01 | 中国石油化工股份有限公司 | Polypropylene composition for plastic inner container of water heater and preparation method thereof |
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2016
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| CN101724203A (en) * | 2008-10-31 | 2010-06-09 | 中国石化上海石油化工股份有限公司 | Polypropylene resin suitable for manufacturing medical infusion bottle by using injection stretch blow moulding process |
| CN102391585A (en) * | 2011-10-08 | 2012-03-28 | 中国石油化工股份有限公司 | Polypropylene material for transparent bottles and preparation method thereof |
| CN103073798A (en) * | 2011-10-25 | 2013-05-01 | 中国石油化工股份有限公司 | Polypropylene composition for plastic inner container of water heater and preparation method thereof |
| CN102532727A (en) * | 2011-12-19 | 2012-07-04 | 江苏金发科技新材料有限公司 | Blow molding grade halogen-free flame-retardant polypropylene material and preparation method thereof |
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|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107880402A (en) * | 2017-11-23 | 2018-04-06 | 上海帆顺包装集团有限公司 | It is adapted to the high transparency high impact resistance polypropylene resin of blow molding process |
| CN107915900A (en) * | 2017-11-23 | 2018-04-17 | 上海帆顺包装集团有限公司 | A kind of suitable blow molding process prepares the acrylic resin of clear hollow product |
| CN108219291A (en) * | 2018-01-09 | 2018-06-29 | 上海帆顺包装集团有限公司 | A kind of acrylic resin and preparation method that hollow product is prepared suitable for blow molding process |
| CN109467824A (en) * | 2018-10-09 | 2019-03-15 | 中国石油化工股份有限公司 | A kind of polypropylene for films composition and preparation method thereof |
| CN115536945A (en) * | 2022-11-03 | 2022-12-30 | 北方华锦化学工业股份有限公司 | Low-melting-index transparent polypropylene resin for blow molding and preparation method thereof |
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