CN114605731A - Flame-retardant polyolefin ionic polymer alloy material for rotational molding and production process thereof - Google Patents
Flame-retardant polyolefin ionic polymer alloy material for rotational molding and production process thereof Download PDFInfo
- Publication number
- CN114605731A CN114605731A CN202210356601.0A CN202210356601A CN114605731A CN 114605731 A CN114605731 A CN 114605731A CN 202210356601 A CN202210356601 A CN 202210356601A CN 114605731 A CN114605731 A CN 114605731A
- Authority
- CN
- China
- Prior art keywords
- parts
- flame retardant
- flame
- rotational molding
- retardant polyolefin
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
Classifications
-
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- 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
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
-
- 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
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a flame-retardant polyolefin ionic polymer alloy material for rotational molding and a production process thereof. The feed is prepared from the following components in parts by mass: 75-90 parts of linear low-density polyethylene, 5-20 parts of high-density polyethylene, 2-5 parts of polypropylene, 5-20 parts of flame retardant, 0.2-1 part of initiator, 5-25 parts of unsaturated resin, 1-5 parts of flame retardant synergist, 1-5 parts of smoke suppressant, 1-5 parts of metal oxide, 0.5-2 parts of lubricant and 0.1-0.8 part of antioxidant. The melt index of the alloy material can be effectively controlled to be between 5 and 10g/10min, and the alloy material is suitable for a rotational molding process; the flame retardant property is good, and the highest flame retardant property can reach UL94V0 grade; the heat distortion temperature is improved by more than 10 ℃ compared with the common flame-retardant cross-linked roll plastic, and the high temperature resistance is better.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a flame-retardant polyolefin ionic polymer alloy material for rotational molding and a production process thereof.
Background
Polyethylene has excellent comprehensive performance and is one of the important raw materials for rotational molding plastic products. The rotational molding product has wider application fields, and relates to the aspects of the countryside, such as mechanical parts, military equipment boxes, food and medicine cold chain boxes, sports and amusement and the like.
The common rotational molding polyethylene has defects in the aspects of flame retardance, high temperature resistance and the like, so that the application of the rotational molding polyethylene to special fields with flame retardance, high temperature resistance and other performance requirements, such as electronic and electric appliance packaging, fuel oil chemical storage and transportation and the like, is greatly limited. Thus, polyethylene must be modified to improve performance. The traditional polyolefin flame-retardant mode has the disadvantages of large dosage of added flame retardant, more product performance reduction, no suitability for rotational molding processing and no suitability for rotational molding product production. In the aspect of high temperature resistance, the common polyethylene can only adapt to the environment with the long-term working temperature of below 70 ℃, and is difficult to adapt to the working environment with higher temperature, so the high temperature resistance is also improved.
Chinese patent CN106867080A discloses a halogen-free flame-retardant antistatic polyethylene composition special for rotational molding and a preparation method thereof, the composition consists of LLDPE, LDPE and halogen-free flame-retardant antistatic master batch, and the halogen-free flame-retardant antistatic master batch consists of conductive carbon black, expandable graphite, phosphorus-nitrogen expansion type flame retardant, antistatic agent, coupling agent, toughening agent, PE wax and antioxidant. The composition of the patent is added with a large amount of 30 to 38 percent of phosphorus-nitrogen intumescent flame retardant, so that the strength of the composition is reduced, and the composition is difficult to adapt to application environments with higher temperature.
Li Yafei is equal to the preparation of V-0 grade flame-retardant crosslinked polyethylene for rotational molding and the performance research thereof on pages 30-33 and 104 of No. 8 of the Plastic industry 2020. It uses decabromodiphenylethane (DBDPE) and antimony trioxide (Sb)2O3) The formed antimony halide flame retardant is used for carrying out flame retardant modification on the crosslinked polyethylene, and V-0 grade flame retardant crosslinked polyethylene for rotational molding is prepared in a laboratory. The polymer has low thermal deformation temperature of only 65 ℃ or below, and is not suitable for application scenes with higher requirements on temperature.
Disclosure of Invention
The invention aims to provide a flame-retardant polyolefin ionic polymer alloy material for rotational molding, which has higher thermal deformation temperature and good high-temperature resistance; the invention also provides a production process thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention relates to a flame-retardant polyolefin ionic polymer alloy material for rotational molding, which is prepared from the following components in parts by mass: 75-90 parts of linear low-density polyethylene, 5-20 parts of high-density polyethylene, 2-5 parts of polypropylene, 5-20 parts of flame retardant, 0.2-1 part of initiator, 5-25 parts of unsaturated resin, 1-5 parts of flame retardant synergist, 1-5 parts of smoke suppressant, 1-5 parts of metal oxide, 0.5-2 parts of lubricant and 0.1-0.8 part of antioxidant.
Wherein:
the Linear Low Density Polyethylene (LLDPE) has a melt index of 1-5g/10min (190 ℃,2.16 kg); the High Density Polyethylene (HDPE) has a melt index of 1-15g/10min (190 ℃,2.16 kg); the melt index of the polypropylene (PP) is 2-5g/10min (190 ℃,2.16 kg).
The flame retardant is brominated styrene-butadiene copolymer (brominated SBS).
The initiator is one or two of diisopropylbenzene peroxide (DCP) or di-tert-butyl peroxide (DTBP).
The unsaturated resin is one or two of ethylene-methacrylic acid copolymer (EMAA) or ethylene-acrylic acid copolymer (EAA).
The flame-retardant synergist is antimony trioxide (Sb)2O3)。
The smoke suppressant is zinc borate.
The metal oxide is one or two of magnesium oxide or calcium oxide.
The lubricant is one or two of zinc stearate or calcium stearate.
The antioxidant is one or two of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (antioxidant 1010) or tri [2, 4-di-tert-butylphenyl ] phosphite ester (antioxidant 168).
The invention relates to a production process of a flame-retardant polyolefin ionic polymer alloy material for rotational molding, which comprises the following steps: adding linear low-density polyethylene, high-density polyethylene, polypropylene, a flame retardant, an initiator, unsaturated resin, a flame-retardant synergist, a smoke suppressant, a metal oxide, a lubricant and an antioxidant into a high-speed mixer according to a ratio, uniformly mixing, and extruding and granulating the mixed materials through a double-screw extruder to obtain the flame-retardant polyolefin ionomer alloy material for rotational molding.
Wherein:
the mixing time is controlled to be 5-10min, and the rotating speed during mixing is 100-1000 rpm; the rotation speed of the extruder is 100-500rpm, and the processing temperature range of the extruder is 130-190 ℃.
The invention has the following beneficial effects:
(1) it is known from the prior art that brominated SBS in polymer is not compatible well with PE. The invention utilizes the double-screw extruder to extrude and granulate, can carry out on-line grafting reaction under the high temperature of the double-screw extruder and the initiating action of the initiator, opens the double bond of the flame retardant brominated SBS so as to graft the flame retardant brominated SBS on the polyethylene macromolecular chain to obtain PE-g-brominated SBS, and effectively and uniformly disperses the flame retardant brominated SBS in the polyethylene matrix, thereby realizing the on-line compatibilization and obtaining the alloy material with better comprehensive mechanical property.
(2) In the prior art, the common polyolefin alloy material has insufficient high temperature resistance. In the production process, in-situ reaction is adopted, the ethylene-methacrylic acid copolymer (EMAA) and/or the ethylene-acrylic acid copolymer (EAA) can react with calcium oxide and/or magnesium oxide at high temperature of an extruder to generate polyacrylate ionic polymer, and the polyacrylate ionic polymer generated in the system greatly improves the thermal deformation temperature of the alloy material.
(3) The rotomoulding polyethylene must have a suitable melt index, generally in the range of 4.0 to 10g/10min (190 ℃,2.16 kg). Under the high-temperature action of calcium oxide and/or magnesium oxide and an extruder, polypropylene is very easy to degrade into polypropylene with lower molecular weight, and the melt index of the alloy material can be adjusted on line, so that the alloy material is suitable for a rotational molding process.
(4) The melt index of the flame-retardant polyolefin ionic polymer alloy material for rotational molding can be effectively controlled to be between 5 and 10g/10min (190 ℃,2.16kg), and the flame-retardant polyolefin ionic polymer alloy material is suitable for rotational molding process; the flame retardant property is good, and the highest flame retardant property can reach UL94V0 grade; the thermal deformation temperature is improved by more than 10 ℃ compared with that of the common flame-retardant cross-linked roll plastic, and the high-temperature resistance is better; and the alloy material is an environment-friendly material which can be recycled.
Detailed Description
The present invention is further described below with reference to examples.
The raw materials used in the examples were as follows:
linear Low Density Polyethylene (LLDPE), Exxon Mobil, No. 1004, melt index 2.0g/10min (190 ℃,2.16 kg);
high Density Polyethylene (HDPE), Yangzhilin, 5000s brand, melt index of 1.2g/10min (190 ℃,2.16 kg);
polypropylene (PP), malted stone, T30S brand, melt index of 3.5g/10min (190 ℃,2.16 kg);
dicumyl peroxide (DCP), a commercially available chemical;
di-tert-butyl peroxide (DTBP), commercially available chemicals;
ethylene-methacrylic acid copolymer (EMAA), exxonmobil, M28N430 brand;
ethylene-acrylic acid copolymer (EAA), dow dupont, 6110 brand;
antimony trioxide (Sb)2O3) Commercial chemicals;
zinc borate, a commercially available chemical; magnesium oxide, commercially available chemicals;
calcium oxide, commercially available chemicals;
zinc stearate, a commercially available chemical;
calcium stearate, commercially available chemicals;
pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (1010), a commercially available chemical;
tris [2, 4-di-tert-butylphenyl ] phosphite (168), a commercially available chemical;
brominated styrene-butadiene copolymer (brominated SBS), available from Hongkong, Inc., flame retardant technology, Inc. The brominated SBS has the following structural formula:
examples 1 to 4
The compositions of the flame retardant polyolefin ionomer alloys for rotational molding in examples 1-4 are shown in Table 1.
Comparative example 1
The flame-retardant polyolefin ionomer alloy material for rotational molding is not added with unsaturated resin, and the rest components are the same as example 1, and the specific components are shown in table 1.
Comparative example 2
The flame-retardant polyolefin ionomer alloy material for rotational molding is not added with metal oxide, and the rest components are the same as example 1, and the specific components are shown in table 1.
Comparative example 3
Commercially available rotomoulded flame retardant cross-linked polyethylene materials were compared and the compositions are shown in table 1. The performance of the flame-retardant polyolefin ionomer alloy for rotational molding in examples 1 to 4 and the performance of the commercially available rotational molding flame-retardant crosslinked polyethylene material in comparative examples 1 to 3 were measured, and the melt index, flame retardancy, heat distortion temperature and recycling performance data are shown in table 1.
TABLE 1 compositions and Performance data for the materials of examples 1-4 and comparative examples 1-3
The compounding ratios of example 1, example 2, example 3 and example 4 in table 1 were weighed out by mass. The weighed raw materials and the auxiliary agent are added into a high-speed mixer to be mixed uniformly, the rotating speed is maintained between 100 and 1000rpm, and the mixing time is controlled to be 5-10 min. And extruding and granulating the mixed material by a double-screw extruder, wherein the rotating speed of the extruder is 300rpm, and the processing temperature interval of the extruder is set to be 130-190 ℃, so as to obtain the flame-retardant polyolefin ionic polymer alloy material for rotational molding.
As can be seen from the performance data in the table 1, the melt index of the alloy material obtained by the formula process can be effectively controlled to be between 5 and 10g/10min (190 ℃,2.16kg), and the alloy material is suitable for the rotational molding process. The flame retardance can reach UL94V0 grade at most. The heat distortion temperature is increased by more than 10 ℃ compared with the common flame-retardant cross-linked plastic rolling material, so that the high-temperature resistance is better. Compared with the flame-retardant cross-linking material for rotational molding which is not recyclable, the alloy material obtained by the formula process is a recyclable environment-friendly material.
Claims (10)
1. The flame-retardant polyolefin ionomer alloy material for rotational molding is characterized by being prepared from the following components in parts by mass: 75-90 parts of linear low-density polyethylene, 5-20 parts of high-density polyethylene, 2-5 parts of polypropylene, 5-20 parts of flame retardant, 0.2-1 part of initiator, 5-25 parts of unsaturated resin, 1-5 parts of flame retardant synergist, 1-5 parts of smoke suppressant, 1-5 parts of metal oxide, 0.5-2 parts of lubricant and 0.1-0.8 part of antioxidant.
2. The flame retardant polyolefin ionomer alloy for rotational molding according to claim 1, wherein: the linear low density polyethylene has a melt index of 1-5g/10 min; the melt index of the high-density polyethylene is 1-15g/10 min; the melt index of the polypropylene is 2-5g/10 min.
3. The flame retardant polyolefin ionomer alloy for rotational molding according to claim 1, wherein: the flame retardant is brominated styrene-butadiene copolymer.
4. The flame retardant polyolefin ionomer alloy for rotational molding according to claim 1, wherein: the initiator is one or two of diisopropylbenzene peroxide or di-tert-butyl peroxide.
5. The flame retardant polyolefin ionomer alloy for rotational molding according to claim 1, wherein: the unsaturated resin is one or two of ethylene-methacrylic acid copolymer or ethylene-acrylic acid copolymer.
6. The flame retardant polyolefin ionomer alloy for rotational molding according to claim 1, wherein: the flame-retardant synergist is antimony trioxide; the smoke suppressant is zinc borate; the metal oxide is one or two of magnesium oxide or calcium oxide.
7. The flame retardant polyolefin ionomer alloy for rotational molding according to claim 1, wherein: the lubricant is one or two of zinc stearate or calcium stearate.
8. The flame retardant polyolefin ionomer alloy for rotational molding according to claim 1, wherein: the antioxidant is one or two of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester or tri [2, 4-di-tert-butylphenyl ] phosphite ester.
9. A process for producing a flame retardant polyolefin ionomer alloy for rotational moulding according to any of claims 1 to 8, characterized in that: adding linear low-density polyethylene, high-density polyethylene, polypropylene, a flame retardant, an initiator, unsaturated resin, a flame-retardant synergist, a smoke suppressant, a metal oxide, a lubricant and an antioxidant into a high-speed mixer according to a ratio, uniformly mixing, and extruding and granulating the mixed material by a double-screw extruder to obtain the flame-retardant polyolefin ionomer alloy material for rotational molding.
10. The process for producing a flame retardant polyolefin ionomer alloy for rotational molding according to claim 9, wherein: the mixing time is controlled to be 5-10min, and the rotating speed during mixing is 100-1000 rpm; the rotation speed of the extruder is 100-500rpm, and the processing temperature range of the extruder is 130-190 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210356601.0A CN114605731A (en) | 2022-03-31 | 2022-03-31 | Flame-retardant polyolefin ionic polymer alloy material for rotational molding and production process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210356601.0A CN114605731A (en) | 2022-03-31 | 2022-03-31 | Flame-retardant polyolefin ionic polymer alloy material for rotational molding and production process thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114605731A true CN114605731A (en) | 2022-06-10 |
Family
ID=81867970
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210356601.0A Pending CN114605731A (en) | 2022-03-31 | 2022-03-31 | Flame-retardant polyolefin ionic polymer alloy material for rotational molding and production process thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114605731A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739946A (en) * | 2013-12-07 | 2014-04-23 | 天津市华鑫达投资有限公司 | High-impact high-stiffness polypropylene rotational molding material and preparation method thereof |
| CN109942730A (en) * | 2019-03-07 | 2019-06-28 | 天津市建筑材料科学研究院有限公司 | A kind of Heterogeneous oxidation prepares brominated styrene-butadiene copolymer method |
| CN110452505A (en) * | 2019-08-27 | 2019-11-15 | 佛山市三水金戈新型材料有限公司 | A kind of thermally conductive polyester composite of high heat resistance and preparation method thereof |
-
2022
- 2022-03-31 CN CN202210356601.0A patent/CN114605731A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739946A (en) * | 2013-12-07 | 2014-04-23 | 天津市华鑫达投资有限公司 | High-impact high-stiffness polypropylene rotational molding material and preparation method thereof |
| CN109942730A (en) * | 2019-03-07 | 2019-06-28 | 天津市建筑材料科学研究院有限公司 | A kind of Heterogeneous oxidation prepares brominated styrene-butadiene copolymer method |
| CN110452505A (en) * | 2019-08-27 | 2019-11-15 | 佛山市三水金戈新型材料有限公司 | A kind of thermally conductive polyester composite of high heat resistance and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112250935B (en) | High-flame-retardant-grade low-smoke halogen-free material and preparation method and application thereof | |
| CN101173074B (en) | Polypropelene composition with scratch resistant capability and processes for producing same | |
| CN109627568B (en) | Polyolefin cable sheath material and preparation method thereof | |
| CN112745570B (en) | Polypropylene halogen-free flame-retardant master batch and preparation method and application thereof | |
| CN108239331B (en) | Thermoplastic halogen-free flame-retardant material and preparation method thereof | |
| CN111171542B (en) | High CTI flame-retardant polycarbonate alloy material and preparation method and application thereof | |
| CN110684344A (en) | Halogen-free flame-retardant nylon composite material and preparation method and application thereof | |
| CN110818997A (en) | Flame-retardant polyethylene cable material and preparation method thereof | |
| CN106995559A (en) | UL94 5VA grades a kind of high GWIT RPPs composition and preparation method thereof | |
| CN114031844B (en) | Halogen-free flame-retardant master batch for continuous long glass fiber reinforced polypropylene and preparation method thereof | |
| CN117534899B (en) | Cold-resistant halogen-free flame-retardant polyolefin cable material and preparation process thereof | |
| CN111019211A (en) | Modified high-density polyethylene composite material and preparation method thereof | |
| CN110713656B (en) | Polypropylene composite material and preparation method thereof | |
| CN102295797B (en) | Zero-halogen flame-retardant polyolefin material and preparation method as well as application thereof | |
| CN112608551A (en) | Halogen-free low-smoke flame-retardant crosslinked polyethylene material and preparation method thereof | |
| CN114605731A (en) | Flame-retardant polyolefin ionic polymer alloy material for rotational molding and production process thereof | |
| CN103881344A (en) | Antistatic halogen-free flame-retardant PC/PBT alloy material and preparation method thereof | |
| CN115368687A (en) | Styrene-polyolefin functional polymer and preparation method thereof | |
| CN113956564A (en) | Anti-dripping low-smoke halogen-free flame-retardant polyolefin oxygen-insulating material easy to process and preparation method thereof | |
| CN110819010A (en) | Halogen-free flame-retardant polypropylene material with ultrahigh specific gravity and preparation method thereof | |
| CN109071892B (en) | Composite polyethylene composition, method of making the same, and articles comprising the same | |
| US20150357081A1 (en) | Resin composition with excellent surface smoothness | |
| CN114276602B (en) | Halogen-free high-flame-retardance polyolefin material and preparation method thereof | |
| CN116041823B (en) | Halogen-free intumescent flame-retardant antistatic thermoplastic elastomer composite foaming material and preparation method thereof | |
| CN114316418B (en) | Low-shrinkage flame-retardant polyethylene composition, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |