CN102516628B - High-density polyethylene composite material and preparation method thereof - Google Patents
High-density polyethylene composite material and preparation method thereof Download PDFInfo
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- CN102516628B CN102516628B CN201110398086.4A CN201110398086A CN102516628B CN 102516628 B CN102516628 B CN 102516628B CN 201110398086 A CN201110398086 A CN 201110398086A CN 102516628 B CN102516628 B CN 102516628B
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- 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
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- 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
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
-
- 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
- B29C2948/92514—Pressure
-
- 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
- B29C2948/92561—Time, e.g. start, termination, duration or interruption
-
- 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
- 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
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
Abstract
The invention is applicable to the technical field of engineering plastics, and provides a high-density polyethylene composite material and a preparation method thereof. The high-density polyethylene composite material utilizes an antidropping agent of a constitutional formula I. By adopting the constitutional formula I, effective flame retardant effect can be realized through fluorine; high flame retardant grade and high chemical property can be realized through Oxazole ring; and the preparation method of the high-density polyethylene composite material is simple to operate, has low cost, and is very suitable for the industrialized production.
Description
Technical field
The invention belongs to engineering plastics field, relate in particular to a kind of high-density polyethylene composite material and preparation method thereof.
Background technology
High density polyethylene(HDPE) (HDPE) is a kind of general synthetic resin of excellent performance, in fields such as industrial or agricultural, national defence, construction industry and daily necessities, all has been widely used.Along with the development of petrochemical complex, HDPE increase of production is very fast, and annual production is at present only lower than Low Density Polyethylene (LDPE) and polyvinyl chloride (PVC).But HDPE oxygen index is very low, flame retardant effect is very poor, has limited its further widespread use.
HDPE is accompanied by the vertical phenomenon of violent melt droplets in combustion processes, need to add a high proportion of fire retardant and anti-dripping agent and could improve this problem.The ptfe micropowder that on market, general anti-dripping agent is surface modification, is subject to the impact of process for modifying surface, and it is high that this type of anti-dripping agent has adding proportion, the shortcoming poor with resin compatible.
Summary of the invention
The object of the present invention is to provide a kind of high-density polyethylene composite material, between the anti-dripping agent that solution prior art middle-high density composite polyethylene material adds and high density polyethylene(HDPE), consistency is poor, the technical problem that mechanical property is low.
The present invention is achieved in that
A kind of high-density polyethylene composite material, comprises the component of following weight percentage:
Described anti-dripping agent has following structural formula I:
And,
Above-specified high density composite polyethylene material preparation method, comprises the steps:
The component of following weight percentage is provided:
Described anti-dripping agent has following structural formula I:
Described component is mixed to get to mixture, described mixture is extruded to processing, obtain high-density polyethylene composite material.
High-density polyethylene composite material of the present invention, is used said structure formula I anti-dripping agent, by fluorine element, effectively plays fire retardation; Tong Guo oxazole heterocycle makes it have higher flame retardant rating and mechanical property simultaneously; High-density polyethylene composite material preparation method of the present invention, simple to operate, with low cost, be very suitable for suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is embodiment of the present invention preparation method schema.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The embodiment of the present invention provides a kind of high-density polyethylene composite material, comprises the component of following parts by weight:
Described anti-dripping agent has following structural formula I:
In the anti-dripping agent that embodiment of the present invention high-density polyethylene composite material is used, contain fluorine element or/and other halogenss, wherein fluorine element content is high, can play very excellent flame retardant properties; Further, in this anti-dripping agent, go back Bao Kuo You oxazole heterocycle, nitrogen element wherein not only has anti-flaming function, also can be capable with the hydrogen atom in high density polyethylene(HDPE) become hydrogen bond crosslinked, and then improved the consistency of anti-dripping agent and high density polyethylene(HDPE), make high-density polyethylene composite material there is higher flame retardant rating and mechanical property simultaneously.
The preparation method of this anti-dripping agent, comprises the steps:
Step 1, supply raw materials:
Provide respectively structural formula to be
compd A and structural formula be
compd B;
Step 2, dehydration reaction:
The compd A and the compd B that by mol ratio, are 2.05～2.1: 1 are added in PPA solvent, at oxygen free condition and temperature, are to react 9～12 hours under 185～195 ℃ of conditions, obtain the anti-dripping agent of structural formula I, and structural formula I is
wherein, X is halogens.
Particularly, in step 1, the name of compd A is called 4 '-halogenated benzoic acid (4-XBA), for example, fluorinated acid, Chlorobenzoic Acid, bromobenzoic acid or iodobenzoic acid, compd A can be from buying and obtain on the market.The name of compd B is called two (3-amino-4-hydroxyphenyl) HFC-236fa (6F-BAHP), and compd B can be from buying and obtain on the market.
Particularly, in step 2, the mol ratio of this compd A and compd B is 2.05～2.1: 1, is preferably 2: 1.
Particularly, this PPA solvent refers to poly phosphoric acid solution, and in this poly phosphoric acid solution, the weight percentage of Vanadium Pentoxide in FLAKES is 85%～90%.The concentration of the available poly phosphoric acid solution of purchasing is less than above-mentioned concentration on the market, above-mentioned weight percentage is by adding Vanadium Pentoxide in FLAKES solid in poly phosphoric acid solution, by oil bath etc., be heated to again thickly, make Vanadium Pentoxide in FLAKES completely be dissolved in poly phosphoric acid solution and obtain.
Particularly, in step 2, the reaction of compd A and compd B is carried out under oxygen free condition, and this oxygen free condition does not limit, and for example, by pass into nitrogen in reactor, makes reactor keep oxygen-free environment.In this step, temperature of reaction is 185～195 ℃, and for example, 190 ℃, the reaction times is 9～12 hours, for example 10 hours.The reaction formula of step 2 is expressed as:
Further, after reaction finishes, liquid cooling after reacting, stopped reaction.Deionized water is injected into the solid product that obtains grey black in reactor, hot-water soak, flushing are until leacheate is neutrality.After activated carbon decolorizing, recrystallization, vacuum-drying, obtain white product, the anti-dripping agent of the structural formula I using in high-density polyethylene composite material of the present invention.
Particularly, in structural formula I, halogens is selected from fluorine, chlorine, bromine or iodine.
Particularly, halogen-free flame retardants is the composite expansion type flame retardant of phosphorus-nitrogen, as 10200, and the place of production: the protruding plastics additive of Town in Shanghai company limited; HFR-041, the place of production; Foshan Wei Kede chemical materials company limited.
Particularly, this lubricant is strong polarity organic molecule, for example, and as ethylene bis-fatty acid amides (TAF, TAS-2A etc.).
Particularly, this oxidation inhibitor does not limit, and for example 1010,186 etc.
Refer to Fig. 1, Fig. 1 shows that the embodiment of the present invention enters high-density polyethylene composite material preparation method schema, comprises the steps:
Step S01, supplies raw materials:
The component of following weight percentage is provided:
Described anti-dripping agent has following structural formula I:
Step S02, extrudes processing:
Described component is mixed to get to mixture, described mixture is extruded to processing, obtain high-density polyethylene composite material.
Particularly, in structural formula I, halogens is selected from fluorine, chlorine, bromine or iodine.
Particularly, halogen-free flame retardants is the composite expansion type flame retardant of phosphorus-nitrogen, as 10200, and the place of production: the protruding plastics additive of Town in Shanghai company limited; HFR-041, the place of production; Foshan Wei Kede chemical materials company limited.
Particularly, this lubricant is strong polarity organic molecule, for example, and as ethylene bis-fatty acid amides (TAF, TAS-2A etc.).
Particularly, this oxidation inhibitor does not limit, and for example 1010,186 etc.
Particularly
Particularly, this anti-dripping agent prepares by preceding method, and the weight percentage of this anti-dripping agent is 0.1%～0.5%, is preferably 0.2%～0.4%.
Concrete, in step S02, the raw material that step S01 is provided mixes, and obtains mixture, then this mixture is melt extruded to processing by twin screw extruder or single screw extrusion machine process, extrudes in treatment step, and processing condition are as follows:
One district temperature 130-140 ℃, two district temperature 170-180 ℃, three district temperature 180-190 ℃, four district temperature 175-185 ℃, head 180-190 ℃, the residence time 1～2min, pressure is 20-30MPa.By extruding processing, cooling, granulation, obtain embodiment of the present invention high-density polyethylene composite material.
Embodiment of the present invention high-density polyethylene composite material preparation method, simple to operate, with low cost, be very suitable for suitability for industrialized production, preparation-obtained high-density polyethylene composite material is used said structure formula I anti-dripping agent, by fluorine element, effectively plays fire retardation; Tong Guo oxazole heterocycle makes it have higher flame retardant rating and mechanical property simultaneously.
Below in conjunction with specific embodiment, above-specified high density composite polyethylene material preparation method is described in detail.
Embodiment mono-
The embodiment of the present invention one high-density polyethylene composite material preparation method, comprises the steps:
It is 83.9% HDPE (being below weight percentage) that weight percentage is provided, the anti-dripping agent of the structural formula I of 15% halogen-free flame retardants 10200,0.1%, 0.5% lubricant, 0.5% oxidation inhibitor;
The HDPE that is 83.9% by weight percentage (being below weight percentage), 15% halogen-free flame retardants 10200, the anti-dripping agent of 0.1% structural formula I, 0.5% lubricant, 0.5% oxidation inhibitor mixes, and the material mixing is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization, obtains high-density polyethylene composite material.Wherein, the temperature setting of the each district of screw rod is respectively: twin screw extruder one district temperature 130-140 ℃, and two district temperature 170-180 ℃, three district temperature 180-190 ℃, four district temperature 175-185 ℃, head 180-190 ℃, the residence time 1～2min, pressure is 20-30MPa.
Embodiment bis-
The embodiment of the present invention two high-density polyethylene composite material preparation methods, comprise the steps:
It is 81.6% HDPE (being below weight percentage) that weight percentage is provided, the anti-dripping agent of the structural formula I of 17% halogen-free flame retardants 10200,0.2%, 0.6% lubricant, 0.6% oxidation inhibitor;
By HDPE weight percentage, be 81.6% (being below weight percentage), halogen-free flame retardants 1020017%, the anti-dripping agent 0.2% of structural formula I, lubricant 0.6%, oxidation inhibitor 0.6% mixes, the material mixing is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes.Wherein, the temperature setting of the each district of screw rod is respectively: twin screw extruder one district temperature 130-140 ℃, and two district temperature 170-180 ℃, three district temperature 180-190 ℃, four district temperature 175-185 ℃, head 180-190 ℃, the residence time 1～2min, pressure is 20-30MPa.
Embodiment tri-
The embodiment of the present invention three high-density polyethylene composite material preparation methods, comprise the steps:
It is 79.3% HDPE (being below weight percentage) that weight percentage is provided, the anti-dripping agent of the structural formula I of 19% halogen-free flame retardants 10200,0.3%, 0.7% lubricant, 0.7% oxidation inhibitor;
By HDPE weight percentage, be 79.3% (being below weight percentage), halogen-free flame retardants 1020019%, the anti-dripping agent 0.3% of structural formula I, lubricant 0.7%, oxidation inhibitor 0.7% mixes, the material mixing is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes.Wherein, the temperature setting of the each district of screw rod is respectively: twin screw extruder one district temperature 130-140 ℃, and two district temperature 170-180 ℃, three district temperature 180-190 ℃, four district temperature 175-185 ℃, head 180-190 ℃, the residence time 1～2min, pressure is 20-30MPa.
Embodiment tetra-
The embodiment of the present invention four high-density polyethylene composite material preparation methods, comprise the steps:
It is 75% HDPE (being below weight percentage) that weight percentage is provided, the anti-dripping agent of the structural formula I of 23% halogen-free flame retardants 10200,0.4%, 0.8% lubricant, 0.8% oxidation inhibitor;
By HDPE weight percentage, be 75% (being below weight percentage), halogen-free flame retardants HFR-04123%, the anti-dripping agent 0.4% of structural formula I, lubricant 0.8%, oxidation inhibitor 0.8% mixes, the material mixing is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes.Wherein, the temperature setting of the each district of screw rod is respectively: twin screw extruder one district temperature 130-140 ℃, and two district temperature 170-180 ℃, three district temperature 180-190 ℃, four district temperature 175-185 ℃, head 180-190 ℃, the residence time 1～2min, pressure is 20-30MPa.
Embodiment five
The embodiment of the present invention five high-density polyethylene composite material preparation methods, comprise the steps:
It is 72.5% HDPE (being below weight percentage) that weight percentage is provided, the anti-dripping agent of the structural formula I of 25% halogen-free flame retardants 10200,0.5%, 1% lubricant, 1% oxidation inhibitor;
By HDPE weight percentage, be 72.5% (being below weight percentage), halogen-free flame retardants HFR-04125%, the anti-dripping agent 0.5% of structural formula I, lubricant 1%, oxidation inhibitor 1% mixes, the material mixing is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes.Wherein, the temperature setting of the each district of screw rod is respectively: twin screw extruder one district temperature 130-140 ℃, and two district temperature 170-180 ℃, three district temperature 180-190 ℃, four district temperature 175-185 ℃, head 180-190 ℃, the residence time 1～2min, pressure is 20-30MPa.
Comparative example:
This comparative example high-density polyethylene composite material preparation method, comprises the steps:
It is 75% HDPE (being below weight percentage) that weight percentage is provided, the commodity anti-dripping agent DB105 of 23% halogen-free flame retardants 10200,0.4%, 0.8% lubricant, 0.8% oxidation inhibitor;
By HDPE weight percentage, be 75% (being below weight percentage), halogen-free flame retardants HFR-04123%, commodity anti-dripping agent DB1050.4%, lubricant 0.8%, oxidation inhibitor 0.8% mixes, the material mixing is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes.Wherein, the temperature setting of the each district of screw rod is respectively: twin screw extruder one district temperature 130-140 ℃, and two district temperature 170-180 ℃, three district temperature 180-190 ℃, four district temperature 175-185 ℃, head 180-190 ℃, the residence time 1～2min, pressure is 20-30MPa.
Performance test:
Tensile strength is tested by ASTM D-638 standard.Specimen types is I type, batten size (mm): (176 ± 2) (length) × (12.6 ± 0.2) (end width) × (3.05 ± 0.2) (thickness), draw speed is 50mm/min;
Flexural strength and modulus in flexure are tested by ASTM D-790 standard.Specimen types is specimen size (mm): (128 ± 2) × (12.67 ± 0.2) × (3.11 ± 0.2), and rate of bending is 20mm/min;
Socle girder notched Izod impact strength is tested by ASTM D-256 standard.Specimen types is I type, specimen size (mm): (63 ± 2) × (12.45 ± 0.2) × (3.1 ± 0.2); Breach type is category-A, and breach residual thickness is 1.9mm;
Flame retardant properties is tested by UL94, test size (mm): (128 ± 2) × (12.67 ± 0.2) × (3.11 ± 0.2), and flame height 20mm, test bars thickness is respectively 3.2mm, 1.6mm and 0.8mm
Embodiment mono-～five and comparative example formula and material property are in Table 1:
Table 1
As can be seen from Table 1, the anti-dripping agent of structural formula I has higher flame retardant effect to HDPE resin, when adding proportion, can effectively suppress the molten of HDPE melt and hang down when above 0.2%, makes the fire-retardant rank of HDPE bring up to V0 by V2.Compare with similar anti-dripping agent on market, homemade anti-dripping agent and resin compatible are good, therefore, compared with making material reach higher fire-retardant rank under few additive, make material have good comprehensive mechanical property simultaneously.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (5)
1. a high-density polyethylene composite material, comprises the component of following weight percentage:
Described anti-dripping agent has following structural formula I:
2. high-density polyethylene composite material as claimed in claim 1, is characterized in that, in described anti-dripping agent, halogens is selected from fluorine, chlorine, bromine or iodine.
3. a high-density polyethylene composite material preparation method, comprises the steps:
The component of following weight percentage is provided:
Described anti-dripping agent has following structural formula I:
Described component is mixed to get to mixture, described mixture is extruded to processing, obtain high-density polyethylene composite material.
4. high-density polyethylene composite material preparation method as claimed in claim 3, is characterized in that, described halogens is selected from fluorine, chlorine, bromine or iodine.
5. high-density polyethylene composite material preparation method as claimed in claim 4, is characterized in that, described in extrude treatment condition and be:
One district temperature 130-140 ℃, two district temperature 170-180 ℃, three district temperature 180-190 ℃, four district temperature 175-185 ℃, head 180-190 ℃, the residence time 1～2min, pressure is 20-30MPa.
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Effective date of registration: 20180105 Address after: 241000 Anhui city of Wuhu Province Economic and Technological Development Zone Dong Liang Road No. 9 Patentee after: Polymer Science (Anhui) New Material Co., Ltd. Address before: Two, C2, A19, 518103 Bridge Fu Qiao third industrial zone, Fuyong street, Baoan District, Guangdong, Shenzhen, China Patentee before: Shenzhen Keju New Material Co., Ltd. |
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