CN103509263A - Environment-friendly adding type polyethylene flame-retardant masterbatch and preparation method thereof - Google Patents
Environment-friendly adding type polyethylene flame-retardant masterbatch and preparation method thereof Download PDFInfo
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- 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
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
- C08L23/286—Chlorinated polyethylene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
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- 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
- C08L23/06—Polyethene
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92609—Dimensions
- B29C2948/92619—Diameter or circumference
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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Abstract
The invention discloses an environment-friendly adding type polyethylene flame-retardant masterbatch. The masterbatch comprises the following raw materials by mass: 10 parts of carrier resin, 15 parts of chlorinated polyethylene, 28 parts of decabromodiphenylethane, 10 parts of antimony trioxide, 3-10 parts of TBC (tri-N-butyl citrate) flame retardant, 12 parts of flame retardant synergist, 5-15 parts of MCA (melamine cyanurate) flame retardant, 8 parts of lubricating agent and 1 part of antioxidant. The polyethylene flame-retardant masterbatch is environment-friendly, non-toxic, clean and sanitary. The flame retardant efficiency is obvious; the processing performance is excellent; when the masterbatch is used for producing polyethylene products, the addition is low, so that the production cost for the polyethylene material can be greatly reduced; the polyethylene flame-retardant masterbatch is suitable for development of enterprises.
Description
Technical field
The present invention relates to polymeric material field, relate in particular to a kind of environmental protection flame retardant polyethylene master batch, the invention still further relates to the preparation method of this environmental protection addition type polyethylene anti-flaming master batch.
Background technology
Polyethylene (PE), due to the superiority of performance, be widely used in fields such as chemical industry, agricultural, building and packings, but its inflammableness is poor, and product exists disaster hidden-trouble, is therefore necessary its flame retardant resistance to carry out study on the modification.In order to improve the flame retardant resistance of polythene material, conventionally people add fire retardant in raw materials for production, yet most of fire retardant is powder, add dust from flying in man-hour, operating environment extreme difference, have a strong impact on processing staff's health, and the volume of powder and resin base material differs larger, density difference great disparity, raw material is difficult to mix.In addition forcing machine, injection moulding machine be to the material limited and equipment vibrations of the mixing property of the heart vertically, powder is easily sunk and causes separated with resin base material, produces segregation phenomenon.Have powder easily to reunite again, also make feeding inaccurate, cause component fluctuation, material property is unstable, is difficult to reach anticipation flame retardant effect.Prior art has by preparing fire-retardant master granule and solves operating environment poor problem, but but there is product bad dispersibility in fire-retardant master granule of the prior art, be difficult to processing, poisonous, flame retardant properties is poor or expensive shortcoming, can not meet client's demand.
Summary of the invention
The object of the invention is to propose a kind of environmental protection addition type polyethylene anti-flaming master batch, this fire-retardant master granule has good dispersion, is easy to processing, environment-protecting asepsis, good flame-retardance energy and the advantage such as cheap.
In order to solve prior art problem, the present invention has designed a kind of environmental protection addition type polyethylene anti-flaming master batch, the raw material of following mass fraction, consists of: 1 part, 10 parts of vector resins, 15 parts of chlorinatedpolyethylenees, 28 parts of TDE, 10 parts of antimonous oxides, 3 ~ 10 parts of TBC fire retardants, 12 parts of fire retarding synergists, 5 ~ 15 parts of MCA fire retardants, 8 parts of lubricants and oxidation inhibitor;
Wherein, described vector resin is any one or two kinds of combination in linear low density polyethylene and vinyl-vinyl acetate copolymer;
Described chlorinatedpolyethylene is that cl content is 70% chlorinatedpolyethylene powder;
Described fire retarding synergist is the mineral substance fire retarding synergist of siliceous, the magnesium elements through modification;
Described TBC fire retardant is that fusing point is three (2,3-dibromopropyl) isocyanuric acid ester white powder that 110 ℃, bromine content are 65%;
Described MCA fire retardant is that size-grade distribution D50 is that 2 ~ 4 μ m, D90 are the melamine cyanurate of 4 ~ 6 μ m and whiteness > 98%.
Described lubricant is any one or several combination in stearic acid, EBS, polyethylene wax, calcium stearate, Zinic stearas and silicone powder.
To be antioxidant 1010 and irgasfos 168 obtain by weight the combination of 1:2 described antioxidant.
A preparation method for environmental protection addition type polyethylene anti-flaming master batch, comprises the following steps:
1) by proportioning, take vector resin, chlorinatedpolyethylene, TDE, antimonous oxide, TBC fire retardant, fire retarding synergist, MCA fire retardant, lubricant and oxidation inhibitor, adopt homogenizer to material stirring 3min;
2) mixed material being joined to surface hardness is in the taper feeding twin screw processed of the via nitride of HRC55 ° ~ HRC58 °;
3) taper feeding twin screw material is out joined and in twin screw extruder, carries out mixing processing, with the laggard row tie rod of water cooling, pelletizing, vibrosieve from, obtain environmental protection flame retardant polyethylene master batch;
Wherein, the diameter of twin screw extruder is that 30 ~ 75mm, length-to-diameter ratio are 44:1, and twin screw extruder temperature is controlled as follows: 100 ~ 115 ℃ of first paragraphs, four sections 140 ~ 150 ℃ of second segments to the, the 5th section 155 ~ 160 ℃, 150 ℃ of heads.
The present invention adopts TDE, TBC fire retardant as main flame retardant, in combustion processes, do not produce poisonous many bromos dibenzo dioxan and many bromos dibenzo furan Nandi, use antimonous oxide as auxiliary flame retardant, improved flame retarding efficiency, adopt cheap fire retarding synergist, MCA fire retardant partly to substitute more expensive antimonous oxide simultaneously, the polyethylene anti-flaming master batch of every production 1t, at least can save 8000 yuan, has improved greatly the competitiveness of product in market.In addition, the synergistic effect effect that described flame-retardant system occurs, can increase substantially the flame retarding efficiency of polyethylene anti-flaming master batch, and the smoke density while also effectively reducing burning plays effect heat insulation, oxygen barrier in combustion processes.
Polyethylene anti-flaming master batch environment-protecting asepsis of the present invention, sanitation and hygiene, flame retardant effect is remarkable, and processing characteristics is good, and simultaneously cheap, while producing for polyethylene product, its addition is little, can significantly reduce the production cost of polythene material, is suitable for enterprise development.The fire retardant that polyethylene anti-flaming master batch of the present invention can be used as in the polyethylene product production processes such as emulational plastic, corrugated tube, mine polyethylene tube, organosilane cross-linked poly-ethylene cable sheath material and casting films is used, Effect on Mechanical Properties to resin is little, the bad phenomenon such as be difficult for occurring layering, decorative pattern after adding and separate out.
Embodiment
The present invention has disclosed a kind of environmental protection addition type polyethylene anti-flaming master batch, the raw material of following mass fraction, consists of: 1 part, 10 parts of vector resins, 15 parts of chlorinatedpolyethylenees, 28 parts of TDE, 10 parts of antimonous oxides, 3 ~ 10 parts of TBC fire retardants, 12 parts of fire retarding synergists, 5 ~ 15 parts of MCA fire retardants, 8 parts of lubricants and oxidation inhibitor.
Fire-retardant master granule of the present invention has good dispersion, is easy to processing, environment-protecting asepsis, good flame-retardance energy and the advantage such as cheap, this fire-retardant master granule carries out granulation after mixing in the ratio of 1:10～15 with Low Density Polyethylene, can obtain the polyethylene anti-flaming material that flame retardant resistance reaches UV94 V-2 level, and the performance of polyethylene anti-flaming material own does not decline, this fire-retardant master granule carries out granulation after mixing in the ratio of 1:4～6 with high density polyethylene(HDPE), can obtain the polyethylene anti-flaming material that flame retardant resistance reaches UV94 V-2 level, and the performance of polyethylene anti-flaming material own does not decline.
In the present invention, in order to wrap fire retardant composition, make fire-retardant master granule can extrude smoothly tie rod and pelletizing, fire-retardant master granule is usingd vector resin as resin base material, and selected vector resin is any one or two kinds of combination in linear low density polyethylene and vinyl-vinyl acetate copolymer.
In the present invention, chlorinatedpolyethylene is that cl content is 70% chlorinatedpolyethylene powder, alternative part vector resin, improve the consistency between each material of fire-retardant master granule, chlorinatedpolyethylene is also a kind of efficient flame-retarding agent, cost ratio TDE is cheap, has also reduced cost when improving flame retarding efficiency.
The present invention is usingd TDE and TBC fire retardant as main flame retardant, using antimonous oxide as auxiliary fire retardant, and be used in conjunction with fire retarding synergist, MCA fire retardant, this kind of flame-retardant system can act synergistically, give the flame retardant properties that fire-retardant master granule is good, also there is the effect that heat insulation, oxygen barrier, cooling, prevention inflammable gas are outwards overflowed simultaneously.
The above-mentioned TBC fire retardant of mentioning is a kind of novel, efficiently, addition type bromide fire retardant, there is good flame retardation effect, volatility is low, consistency is good, durable, fast light, the characteristic such as water-fast and nontoxic, good with matrix resin and chlorinatedpolyethylene consistency, can improve the processing fluidity of product, in bromine antimony flame-retardant system, add TBC fire retardant, reduced the addition of bromine antimony fire retardant, reduced cost, and contribute to the raising of flame retarding efficiency, it is 110 ℃ that TBC fire retardant of the present invention is preferably fusing point, bromine content be 65% three (2, 3-dibromopropyl) isocyanuric acid ester white powder.
The above-mentioned MCA of mentioning fire retardant is that size-grade distribution D50 is that 2 ~ 4 μ m, D90 are the melamine cyanurate of 4 ~ 6 μ m and whiteness > 98%; Fire retarding synergist is the mineral substance fire retarding synergist that contains silicon, magnesium elements through modification, this mineral substance fire retarding synergist can be organism, also can be inorganics, described modification processing treatment is prior art, synergistic flame retardant can catch the free radical in combustion reactions in combustion processes, thereby stop the flame density of flame transmission ，Shi combustion zone to decline, finally make combustion velocity decline until stop.Fire retarding synergist and MCA fire retardant are cheap, in the situation that do not affect the flame retardant properties of fire-retardant master granule, can also partly replace expensive antimonous oxide, reduce the production cost of polythene material.
In order to reduce the surfaceness of the polyethylene anti-flaming master batch of extruding, improve dispersiveness and the processibility of master batch, the present invention is also added with lubricant, lubricant is selected from stearic acid, EBS, polyethylene wax, calcium stearate, Zinic stearas and silicone powder, as a kind of embodiment of the present invention, mentioned lubricant can a kind of independent use, is also several being used in combination.
In order to improve processing stability, thermotolerance and the ageing resistance of polyethylene anti-flaming master batch, the present invention is also added with oxidation inhibitor, and antioxidant is the combination of antioxidant 1010 and irgasfos 168, is specially antioxidant 1010 and irgasfos 168 by weight the combination of 1:2.
Another kind of object of the present invention is to propose a kind of preparation method of environmental protection addition type polyethylene anti-flaming master batch, this preparation method comprises step: 1) by recipe ratio, take vector resin, chlorinatedpolyethylene, TDE, antimonous oxide, TBC fire retardant, fire retarding synergist, MCA fire retardant, lubricant and oxidation inhibitor, adopt homogenizer to material stirring 3min; 2) mixed material is passed in the back taper hopper that stirring rake is installed by connecting tube, this back taper hopper is stainless steel hopper, the object that increases stirring rake is to be further uniformly mixed, make each raw material more even, can prevent from producing because powder the phenomenon of the not blanking of building bridge, and then to pass into surface hardness be the two feed screws of taper that the via nitride of HRC55 ° ~ HRC58 ° is processed, with the two feed screws of taper, replace common parallel double feed screw, better transferring raw material, guarantees that feeding is even; 3) the two feed screws of taper material is out passed in twin screw extruder and carries out mixing processing, with the laggard row tie rod of water cooling, pelletizing, vibrosieve from, obtain environmental protection flame retardant polyethylene master batch; Wherein, the diameter of twin screw extruder is that 30 ~ 75mm, length-to-diameter ratio are 44:1, twin screw extruder temperature is controlled as follows: 100 ~ 115 ℃ of first paragraphs, four sections 140 ~ 150 ℃ of second segments to the, the 5th section 155 ~ 160 ℃, 150 ℃ of heads, twin screw extruder of the present invention can be realized good effect at lower temperature, lower extrusion temperature, both can strengthen the shearing melting effect between each material, can make again extruder barrel temperature unlikely too high and cause that part fire retardant decomposes.
Below by specific embodiment, the present invention is described in further detail.
Embodiment 1 is the preparation method of environmental protection addition type polyethylene anti-flaming master batch of the present invention, the polyethylene anti-flaming material of embodiment 2,3 for adopting the environmental protection addition type polyethylene anti-flaming master batch of embodiment 1 gained to prepare, the polyethylene anti-flaming material of comparative example 1,2 for adopting powder fire retardant to prepare.
Embodiment 1
A kind of preparation method of environmental protection addition type polyethylene anti-flaming master batch, this preparation method comprises step: 1) by recipe ratio, take 1 part, 10 parts of vector resins, 15 parts of chlorinatedpolyethylenees, 28 parts of TDE, 10 parts of antimonous oxides, 3 ~ 10 parts of TBC fire retardants, 12 parts of fire retarding synergists, 5 ~ 15 parts of MCA fire retardants, 8 parts of lubricants and oxidation inhibitor, adopt homogenizer to material stirring 3min; 2) mixed material is passed in the back taper hopper that stirring rake is installed by connecting tube, this back taper hopper is stainless steel hopper, the object that increases stirring rake is to be further uniformly mixed, make each raw material more even, prevent from producing because powder the phenomenon of the not blanking of building bridge, and then to pass into surface hardness be the two feed screws of taper that the via nitride of HRC55 ° ~ HRC58 ° is processed, with the two feed screws of taper, replace common parallel double feed screw, better transferring raw material, guarantees that feeding is even; 3) the two feed screws of taper material is out passed in twin screw extruder and carries out mixing processing, with the laggard row tie rod of water cooling, pelletizing, vibrosieve from, obtain environmental protection flame retardant polyethylene master batch; Wherein, the diameter of twin screw extruder is that 30 ~ 75mm, length-to-diameter ratio are 44:1, and twin screw extruder temperature is controlled as follows: 100 ~ 115 ℃ of first paragraphs, four sections 140 ~ 150 ℃ of second segments to the, the 5th section 155 ~ 160 ℃, 150 ℃ of heads.
Embodiment 2
The present embodiment polyethylene anti-flaming material is mixed to get by following parts by weight proportioning: Low Density Polyethylene 2420H(LDPE 2420H) 90.5 parts, 9 parts of fire-retardant master granules, 0.5 part of lubricant.
Embodiment 3
The present embodiment polyethylene anti-flaming material is mixed to get by following parts by weight proportioning: 83.5 parts of high density polyethylene(HDPE) HMA035 (HDPE HMA035), 16 parts of fire-retardant master granules, 0.5 part of lubricant.
Comparative example 1
This comparative example polyethylene anti-flaming material is mixed to get by following parts by weight proportioning: Low Density Polyethylene 2420H(LDPE 2420H) 90.6 parts, 5.7 parts of TDE, 1.7 parts of antimonous oxides, 1.3 parts of fire retarding synergists, 0.5 part of lubricant, 0.2 part, oxidation inhibitor.
Comparative example 2
This comparative example polyethylene anti-flaming material is mixed to get by following parts by weight proportioning: 81.8 parts of high density polyethylene(HDPE) HMA035 (HDPE HMA035), 12 parts of TDE, 3.5 parts of antimonous oxides, 2 parts of fire retarding synergists, 0.5 part of lubricant, 0.2 part, oxidation inhibitor.
Performance to above-described embodiment 2,3 and comparative example 1,2 gained polyethylene anti-flaming materials detects, adopt CG110E horizontal injection machine injection molding standard test specimen, molding technological condition: 150/155/165/170 ℃ of injection temperature (charging opening) (nozzle), injection pressure 50MPa, dwell time 12s; Cooling time 8s.Test result is as shown in table 1, and adopts with the following method and test:
Tensile strength and elongation at break: according to ASTM D-638 standard, carry out.
Notch shock performance: carry out according to ASTM D-256 standard.
Melting index: undertaken by ASTM D-1238 standard.
Flame retardant resistance: vertical combustion performance, by UL94 vertical combustion standard, to test, batten thickness is 1.6mm and 3.2mm.
The performance comparison of table 1 fire-retardant polyethylene material
As shown in Table 1, reach same flame retardant effect (comprise and prolong the combustion time), the amount of the fire-retardant master granule adding is more lower slightly than adding fire retardant, and the ratio of the actual fire retardant in master batch interpolation powder fire retardant is much lower, the good flame retardation effect of surface flame-retardant master batch, while producing the polyethylene anti-flaming material of same output, required fire-retardant master granule amount is few, greatly reduce production cost, and property retention is good, production process is difficult for causing environmental pollution.
According to the elaboration in above specification sheets, those skilled in the art in the invention can also carry out suitable change and modification to above-mentioned embodiment.Therefore, the content of mentioning in above-described embodiment is not limitation of the invention, is not departing under the prerequisite of inventive concept of the present invention, and any apparent replacement is all within protection scope of the present invention.
Claims (4)
1. an environmental protection addition type polyethylene anti-flaming master batch, is comprised of the raw material of following mass fraction: 1 part, 10 parts of vector resins, 15 parts of chlorinatedpolyethylenees, 28 parts of TDE, 10 parts of antimonous oxides, 3 ~ 10 parts of TBC fire retardants, 12 parts of fire retarding synergists, 5 ~ 15 parts of MCA fire retardants, 8 parts of lubricants and oxidation inhibitor;
Wherein, described vector resin is any one or two kinds of combination in linear low density polyethylene and vinyl-vinyl acetate copolymer;
Described chlorinatedpolyethylene is that cl content is 70% chlorinatedpolyethylene powder;
Described fire retarding synergist is the mineral substance fire retarding synergist of siliceous, the magnesium elements through modification;
Described TBC fire retardant is that fusing point is three (2,3-dibromopropyl) isocyanuric acid ester white powder that 110 ℃, bromine content are 65%;
Described MCA fire retardant is that size-grade distribution D50 is that 2 ~ 4 μ m, D90 are the melamine cyanurate of 4 ~ 6 μ m and whiteness > 98%.
2. environmental protection addition type polyethylene anti-flaming master batch according to claim 1, is characterized in that: described lubricant is any one or several combination in stearic acid, EBS, polyethylene wax, calcium stearate, Zinic stearas and silicone powder.
3. environmental protection addition type polyethylene anti-flaming master batch according to claim 1, is characterized in that: to be antioxidant 1010 and irgasfos 168 obtain by weight the combination of 1:2 described antioxidant.
4. according to a preparation method for the environmental protection addition type polyethylene anti-flaming master batch described in any one in claims 1 to 3, comprise the following steps:
1) by proportioning, take vector resin, chlorinatedpolyethylene, TDE, antimonous oxide, TBC fire retardant, fire retarding synergist, MCA fire retardant, lubricant and oxidation inhibitor, adopt homogenizer to material stirring 3min;
2) mixed material being joined to surface hardness is in the taper feeding twin screw processed of the via nitride of HRC55 ° ~ HRC58 °;
3) taper feeding twin screw material is out joined and in twin screw extruder, carries out mixing processing, with the laggard row tie rod of water cooling, pelletizing, vibrosieve from, obtain environmental protection flame retardant polyethylene master batch;
Wherein, the diameter of twin screw extruder is that 30 ~ 75mm, length-to-diameter ratio are 44:1, and twin screw extruder temperature is controlled as follows: 100 ~ 115 ℃ of first paragraphs, four sections 140 ~ 150 ℃ of second segments to the, the 5th section 155 ~ 160 ℃, 150 ℃ of heads.
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Cited By (6)
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| CN106009176A (en) * | 2016-06-29 | 2016-10-12 | 泉州市东盛塑料制品有限公司 | Polyethylene flame-retardant modified master batch and preparation method thereof |
| CN109735913A (en) * | 2019-01-21 | 2019-05-10 | 江苏纵横优仪人造草坪有限公司 | A kind of fire-retardant combination and preparation method thereof, artificial grass filaments, artificial grassplot back glue and chinampa |
| CN109971058A (en) * | 2019-03-22 | 2019-07-05 | 广东聚石化学股份有限公司 | A kind of fire-retardant polyethylene material and preparation method thereof |
| CN114044954A (en) * | 2021-10-20 | 2022-02-15 | 成都金发科技新材料有限公司 | Flame-retardant polyethylene material and preparation method and application thereof |
| CN114773712A (en) * | 2022-05-24 | 2022-07-22 | 三杰节能新材料股份有限公司 | Formula and manufacturing method of low-temperature-resistant flame-retardant outer protective pipe |
| CN116948289A (en) * | 2023-08-04 | 2023-10-27 | 惠州国森灯树有限公司 | Integrated injection molding Christmas tree and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106009176A (en) * | 2016-06-29 | 2016-10-12 | 泉州市东盛塑料制品有限公司 | Polyethylene flame-retardant modified master batch and preparation method thereof |
| CN109735913A (en) * | 2019-01-21 | 2019-05-10 | 江苏纵横优仪人造草坪有限公司 | A kind of fire-retardant combination and preparation method thereof, artificial grass filaments, artificial grassplot back glue and chinampa |
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| CN109971058B (en) * | 2019-03-22 | 2021-07-06 | 广东聚石化学股份有限公司 | Flame-retardant polyethylene material and preparation method thereof |
| CN114044954A (en) * | 2021-10-20 | 2022-02-15 | 成都金发科技新材料有限公司 | Flame-retardant polyethylene material and preparation method and application thereof |
| CN114773712A (en) * | 2022-05-24 | 2022-07-22 | 三杰节能新材料股份有限公司 | Formula and manufacturing method of low-temperature-resistant flame-retardant outer protective pipe |
| CN116948289A (en) * | 2023-08-04 | 2023-10-27 | 惠州国森灯树有限公司 | Integrated injection molding Christmas tree and preparation method thereof |
| CN116948289B (en) * | 2023-08-04 | 2024-02-13 | 惠州国森灯树有限公司 | Integrated injection molding Christmas tree and preparation method thereof |
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