CN104744783A - High-efficient flame-retardant anti-photooxidation polyethylene and preparation method thereof - Google Patents
High-efficient flame-retardant anti-photooxidation polyethylene and preparation method thereof Download PDFInfo
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- CN104744783A CN104744783A CN201510125477.7A CN201510125477A CN104744783A CN 104744783 A CN104744783 A CN 104744783A CN 201510125477 A CN201510125477 A CN 201510125477A CN 104744783 A CN104744783 A CN 104744783A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 158
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 146
- -1 polyethylene Polymers 0.000 title claims abstract description 62
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 61
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 61
- 238000007539 photo-oxidation reaction Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 48
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims abstract description 33
- PVKCVCDTYNNNOG-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine;hydrobromide Chemical compound [Br-].NC1=NC(N)=[NH+]C(N)=N1 PVKCVCDTYNNNOG-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 18
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 18
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 15
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 15
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 12
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 12
- 239000000155 melt Substances 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 14
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 12
- 150000001412 amines Chemical class 0.000 claims description 11
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- ATDGTVJJHBUTRL-UHFFFAOYSA-N cyanogen bromide Chemical compound BrC#N ATDGTVJJHBUTRL-UHFFFAOYSA-N 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 36
- 238000001746 injection moulding Methods 0.000 description 32
- 229920003023 plastic Polymers 0.000 description 23
- 239000004033 plastic Substances 0.000 description 23
- 238000005520 cutting process Methods 0.000 description 16
- 239000011521 glass Substances 0.000 description 16
- 238000002347 injection Methods 0.000 description 16
- 239000007924 injection Substances 0.000 description 16
- 238000002156 mixing Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000005303 weighing Methods 0.000 description 16
- 229910052736 halogen Inorganic materials 0.000 description 9
- 150000002367 halogens Chemical class 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 230000000979 retarding effect Effects 0.000 description 4
- 0 C1C(*C2)*C2*1 Chemical compound C1C(*C2)*C2*1 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PFYHYHZGDNWFIF-UHFFFAOYSA-N (+)-DMDP Natural products OCC1NC(CO)C(O)C1O PFYHYHZGDNWFIF-UHFFFAOYSA-N 0.000 description 1
- PFYHYHZGDNWFIF-KVTDHHQDSA-N 2,5-bis(hydroxymethyl)-3,4-dihydroxypyrrolidine Chemical compound OC[C@H]1N[C@H](CO)[C@@H](O)[C@@H]1O PFYHYHZGDNWFIF-KVTDHHQDSA-N 0.000 description 1
- PFYHYHZGDNWFIF-OMMKOOBNSA-N 2R,5R-Dihydroxymethyl-3R,4R-dihydroxy-pyrrolidine Natural products OC[C@@H]1N[C@@H](CO)[C@H](O)[C@@H]1O PFYHYHZGDNWFIF-OMMKOOBNSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical class [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000003042 antagnostic effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910001503 inorganic bromide Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34922—Melamine; Derivatives thereof
-
- 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
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
- C08K5/5357—Esters of phosphonic acids cyclic
-
- 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
-
- 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
- C08L2207/066—LDPE (radical process)
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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)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to high-efficient flame-retardant anti-photooxidation polyethylene and a preparation method thereof. The high-efficient flame-retardant anti-photooxidation polyethylene comprises the following components in percentage by weight: 85-95% of polyethylene, 2-8% of melamine hydrobromide, 2.5-5% of a phosphonate flame retardant and 0.5-2% of a flame retardant synergist, wherein the polyethylene is one or more of high-density polyethylene, low-density polyethylene and linear low-density polyethylene. According to the preparation method, a multielement collaborative composite flame-retardant system formed by melamine hydrobromide, the phosphonate flame retardant and the flame retardant synergist is mixed with the polyethylene, the flame-retardant efficiency of the material is improved, and the anti-photooxidation capacity of the material is also improved; meanwhile, the preparation method has the characteristics that the raw materials are easily available, the process is simple and feasible, the production operation is safe, and the like, the flame-retardant polyethylene is good in stability and excellent in comprehensive performance, maintains a good yellow color index, and has a good application prospect.
Description
Technical Field
The invention relates to the technical field of materials, in particular to high-efficiency flame-retardant photooxidation-resistant polyethylene and a preparation method thereof.
Background
Polyethylene is the thermoplastic plastic with the largest consumption in the current plastics, has excellent electrical insulation, low temperature resistance, easy processing and forming, sufficient mechanical property, excellent chemical stability and dielectric property, and is widely applied to the manufacture of films, daily products, pipes, insulating materials and sheathing materials of electric wires and cables. The development of the plastic industry makes people have higher and higher requirements on various properties of plastic products, and higher requirements on fire safety of the plastic products are put forward, and particularly in the aspects of wires, cables, indoor building materials and the like, the plastic products not only need to be flame retardant, but also need to be halogen-free and pollution-free. However, the oxygen index of polyethylene is very low, only 17.4, and the polyethylene belongs to flammable materials, thereby greatly limiting the wider application of polyethylene. Polyethylene is easy to generate thermo-oxidative aging under the action of heat in air, so that the service performance of the polymer is gradually reduced, and the service value of the polymer is lost. It is believed that light is a main factor causing aging degradation in outdoor atmospheric environment, and improving the photo-oxidation resistance of polyethylene materials helps to improve the mechanical properties, heat resistance, aging resistance and the like.
The flame retarding of polyethylene is mainly realized by adding flame retardant and certain flame retarding materials, namely, the flame retardant and other additives are added and mixed together when plastics are compounded. Depending on the type of the flame retardant used, they can be classified into halogen-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, and the like. The halogen flame retardant flame-retardant polyethylene has excellent flame-retardant performance, small addition amount and good compatibility with polyethylene, but generates a large amount of smoke and toxic and corrosive hydrogen halide gas when the material is combusted, thereby not only hindering rescue work, but also corroding instruments and equipment and generating so-called secondary disasters. The use of halogen-containing flame retardants in polyethylene materials is currently being more and more limited, but because of the high flame retardancy of halogen flame retardants, especially bromine flame retardants, many high-efficiency flame retardant systems at present still require halogen flame retardants, and melamine hydrobromide flame retardants developed in recent years have low toxicity per se and high thermal stability due to the fact that they are inorganic bromides, and thus are receiving much attention. Compared with the traditional flame retardant (such as halide/Sb 2O3), the red phosphorus serving as the phosphorus flame retardant has small smoke quantity, low toxicity and wide application range, can be used independently, and can also be used together with other flame retardants. The dosage is small, the flame retardant effect is good, and the durability is good. However, red phosphorus is directly used for flame retarding of polyethylene, and has large addition amount and poor compatibility with resin, thereby limiting the application. The nitrogen flame retardant has better flame retardant performance in polyurethane and polyamide. But the effect of flame retarding polyethylene by using the nitrogen flame retardant alone is not good. The flame retardant is caused by poor char forming effect, and the flame retardant has good flame retardant effect when being combined with an intumescent flame retardant system formed by a phosphorus-containing flame retardant.
It is known that, in the case of conventional systems, the halogen-containing flame retardants greatly reduce their stability against light oxidation. This is due to the antagonistic action between the halogen flame retardant and the hindered amine light stabilizer. While Flamestab NOR 116 is itself an N-alkoxy hindered amine, an excellent light stabilizer. The advantage of this is that its light stability is maintained when combined with halogen containing flame retardants, as compared to conventional hindered amine light stabilizers. The reason for this is that the interaction of the N-alkoxy hindered amine with the halogen is small. For example, for PP fibers, the Flamestab NOR 116+ uv absorber system can extend the lifetime 2-3 times longer than the conventional system (hindered amine + uv absorber).
Besides good light stability, the Flamestab NOR 116 is a good long-acting heat stabilizer, has small influence on the physical and mechanical properties of a base material, has excellent compatibility with polymers and has high extraction resistance; can be conveniently processed in a melting way, and has the characteristics of safe use, excellent cost performance and the like. The phosphonate flame retardant 3, 9-dimethyl-3, 9-dioxo-2, 4, 8, 10-tetraoxa-3, 9-diphosphodispiro [5.5] undecane (DMDP) has a six-membered spiro structure, contains no hydroxyl group, has high phosphorus content, and has good thermal stability and char formation.
Disclosure of Invention
The invention aims to solve the technical problem of providing high-efficiency flame-retardant photooxidation-resistant polyethylene and a preparation method thereof aiming at the defects in the prior art.
The technical scheme adopted by the invention for solving the technical problems is as follows:
constructing a high-efficiency flame-retardant anti-photooxidation polyethylene, wherein the high-efficiency flame-retardant anti-photooxidation polyethylene comprises the following components in percentage by weight: 85-95% of polyethylene, 2-8% of melamine cyanurate, 2.5-5% of phosphonate flame retardant and 0.5-2% of flame-retardant synergist.
The high-efficiency flame-retardant anti-photooxidation polyethylene is one or a mixture of two or more of high-density polyethylene, low-density polyethylene and linear low-density polyethylene.
The invention relates to high-efficiency flame-retardant photooxidation-resistant polyethylene, wherein the structural formula of melamine hydrobromide is as follows:
the invention relates to high-efficiency flame-retardant anti-photooxidation polyethylene, wherein a phosphonate flame retardant is 3, 9-dimethyl-3, 9-dioxo-2, 4, 8, 10-tetraoxa-3, 9-diphosphodispiro [5.5] undecane, and the structural formula is as follows:
the high-efficiency flame-retardant anti-photooxidation polyethylene is characterized in that the flame-retardant synergist is an N-alkoxy hindered amine flame retardant.
The high-efficiency flame-retardant anti-photooxidation polyethylene disclosed by the invention has a polyethylene content of 88-93%.
The high-efficiency flame-retardant photooxidation-resistant polyethylene disclosed by the invention is characterized in that the melamine cyanurate content is 3-6%.
The high-efficiency flame-retardant and anti-photooxidation polyethylene provided by the invention has the advantage that the content of the phosphonate flame retardant is 3-4%.
The high-efficiency flame-retardant anti-photooxidation polyethylene provided by the invention has a melt index MI of 20g/10min, and a melt index MI of 18g/10 min.
The invention also provides a preparation method of the high-efficiency flame-retardant photooxidation-resistant polyethylene, which comprises the following steps:
A. premixing: sequentially adding polyethylene, melamine, cyanobromide, phosphonate flame retardant and flame retardant synergist into a high-speed mixer for premixing;
B. and (3) extruding and granulating: adding the premixed materials in the step A into a double-screw extruder for extrusion granulation, and cooling and granulating to obtain the required high-efficiency flame-retardant anti-photooxidation polyethylene material; wherein,
the polyethylene is one or a mixture of two or more of high-density polyethylene, low-density polyethylene and linear low-density polyethylene;
the structural formula of the melamine hydrobromide is as follows:
the phosphonate flame retardant is 3, 9-dimethyl-3, 9-dioxo-2, 4, 8, 10-tetraoxa-3, 9-diphosphodispiro [5.5] undecane;
the flame-retardant synergist is an N-alkoxy hindered amine flame retardant.
The invention has the beneficial effects that: by adopting a multi-element synergistic composite flame-retardant system of melamine hydrobromide, phosphonate flame retardant and flame-retardant synergist to mix with polyethylene, the flame-retardant efficiency of the material is improved, and the light-oxygen resistance of the material can also be improved; meanwhile, the flame-retardant polyethylene has the characteristics of easily obtained raw materials, simple and convenient process, safe production operation and the like, has good stability and excellent comprehensive performance, keeps good yellow index, and has good application prospect.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that the following examples are only illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
In the following examples, the polyethylene is one or a mixture of two or more of high density polyethylene, low density polyethylene and linear low density polyethylene. Wherein the melt index MI of the high-density polyethylene is 20g/10min, and the melt index MI of the low-density polyethylene is 18g/10 min.
In the following examples, melamine hydrobromide has the formula:
in the following examples, 3, 9-dimethyl-3, 9-dioxo-2, 4, 8, 10-tetraoxa-3, 9-diphosphodispiro [5.5] undecane, which is commercially available, is preferably used as the phosphonate flame retardant, but other commercially available phosphonate flame retardants may also be used.
In the following examples, the flame retardant synergist is preferably an N-alkoxy hindered amine flame retardant, preferably N-alkoxy hindered amine flame retardant NOR 116 from BASF.
In the following examples, the yellow index is represented by the difference between the yellow index of the sample piece measured and a standard reference, using a specific standard white plate as a reference.
In the following examples, the flame retardant rating refers to the property of a substance or the material after treatment for obviously delaying the flame spread, and according to the rating system, the flame retardant rating of the plastic is gradually increased from HB, V-2, V-1 to V-0. Wherein, 1, HB: the lowest flame retardant rating in the UL94 standard requires a burn rate of less than 40 millimeters per minute for samples 3 to 13 millimeters thick; a sample less than 3 mm thick with a burning rate less than 70 mm per minute; or extinguished before the 100 mm mark. 2. V-2: after two 10 second burn tests on the samples, the flame extinguished within 60 seconds and the combustibles could have fallen. 3. V-1: after two 10 second burn tests on the samples, the flame extinguished within 60 seconds and no combustibles could fall. 4. V-0: after two 10 second burn tests on the samples, the flame extinguished within 30 seconds and no combustibles could fall.
Example 1
Weighing High Density Polyethylene (HDPE) (the melt index MI is 20g/10min) accounting for 85% of the total weight of the materials, 8% of melamine hydrobromide, 5% of phosphonate flame retardant and 2% of flame retardant synergist, uniformly mixing, continuously and uniformly adding the materials into a double-screw extruder by using a double-screw feeder, cooling extruded strips by using a cold water tank, and then cutting the materials to obtain the product. And (3) placing the product into an oven, and then performing injection molding by using a plastic injection molding machine to obtain a standard sample strip. The injection molded bars were immediately placed in a glass desiccator at room temperature for at least 24h before performance testing. The test result shows that the flame retardant rating of the product can reach UL94V-0(3.2mm), and the yellow index (1000h) is 0.77.
Example 2
Weighing 88 percent of Low Density Polyethylene (LDPE) (the melt index MI is 18g/10min) accounting for the total weight percent of the materials, 6 percent of melamine hydrobromide, 4 percent of phosphonate flame retardant and 2 percent of flame retardant synergist, uniformly mixing, continuously and uniformly adding the mixture into a double-screw extruder by using a double-screw feeder, cooling extruded strips by a cold water tank, and then cutting the materials to obtain the product. And (3) placing the product into an oven, and then performing injection molding by using a plastic injection molding machine to obtain a standard sample strip. The injection molded bars were immediately placed in a glass desiccator at room temperature for at least 24h before performance testing. The test result shows that the flame retardant rating of the product can reach UL94V-1(3.2mm), and the yellow index (1000h) is 0.62.
Example 3
Weighing 91 percent of linear low density polyethylene (melt index MI is 17g/10min), 4 percent of melamine hydrobromide, 3 percent of phosphonate flame retardant and 2 percent of flame retardant synergist by weight percent of the total weight of the materials, uniformly mixing, continuously and uniformly adding the materials into a double-screw extruder by using a double-screw feeder, cooling extruded strips by a cold water tank, and then cutting the materials to obtain the product. And (3) placing the product into an oven, and then performing injection molding by using a plastic injection molding machine to obtain a standard sample strip. The injection molded bars were immediately placed in a glass desiccator at room temperature for at least 24h before performance testing. The test result shows that the flame retardant rating of the product can reach UL94V-1(3.2mm), and the yellow index (1000h) is 0.69.
Example 4
Weighing 93 percent of high-density polyethylene (the melt index MI is 20g/10min), 3 percent of melamine hydrobromide, 3.5 percent of phosphonate flame retardant and 0.5 percent of flame retardant synergist which account for the total weight percent of the materials, uniformly mixing, continuously and uniformly adding the materials into a double-screw extruder by using a double-screw feeder, cooling extruded strips by a cold water tank, and cutting to obtain the product. And (3) placing the product into an oven, and then performing injection molding by using a plastic injection molding machine to obtain a standard sample strip. The injection molded bars were immediately placed in a glass desiccator at room temperature for at least 24h before performance testing. The test result shows that the flame retardant rating of the product can reach UL94V-2(3.2mm), and the yellow index (1000h) is 1.36.
Example 5
Weighing a mixture of low-density polyethylene (with a melt index MI of 18g/10min) and linear low-density polyethylene (with a melt index MI of 17g/10min) which account for 94 percent of the total weight of the materials, 3 percent of melamine hydrobromide, 2.5 percent of phosphonate flame retardant and 0.5 percent of flame retardant synergist, uniformly mixing, continuously and uniformly adding the mixture into a double-screw extruder by using a double-screw feeder, cooling extruded strips by a cold water tank, and then cutting to obtain the product. And (3) placing the product into an oven, and then performing injection molding by using a plastic injection molding machine to obtain a standard sample strip. The injection molded bars were immediately placed in a glass desiccator at room temperature for at least 24h before performance testing. The test result shows that the flame retardant rating of the product can reach UL94V-2(3.2mm), and the yellow index (1000h) is 1.50.
Example 6
Weighing linear low-density polyethylene (the melt index MI is 17g/10min) accounting for 94 percent of the total weight of the materials, 2 percent of melamine hydrobromide, 3.5 percent of phosphonate flame retardant and 0.5 percent of flame retardant synergist, uniformly mixing, continuously and uniformly adding the materials into a double-screw extruder by using a double-screw feeder, cooling extruded strips by a cold water tank, and cutting to obtain the product. And (3) placing the product into an oven, and then performing injection molding by using a plastic injection molding machine to obtain a standard sample strip. The injection molded bars were immediately placed in a glass desiccator at room temperature for at least 24h before performance testing. The test result shows that the flame retardant rating of the product can reach UL94V-2(3.2mm), and the yellow index (1000h) is 1.40.
Example 7
Weighing a mixture of high-density polyethylene (with a melt index MI of 20g/10min) and low-density polyethylene (with a melt index MI of 18g/10min) accounting for 86 percent of the total weight of the materials, 7.75 percent of melamine hydrobromide, 5 percent of phosphonate flame retardant and 1.25 percent of flame retardant synergist, uniformly mixing, continuously and uniformly adding the mixture into a double-screw extruder by using a double-screw feeder, cooling extruded strips by a cold water tank, and then cutting to obtain the product. And (3) placing the product into an oven, and then performing injection molding by using a plastic injection molding machine to obtain a standard sample strip. The injection molded bars were immediately placed in a glass desiccator at room temperature for at least 24h before performance testing. The test result shows that the flame retardant rating of the product can reach UL94V-0(3.2mm), and the yellow index (1000h) is 1.13.
Example 8
Weighing low-density polyethylene (the melt index MI is 18g/10min) accounting for 90 percent of the total weight of the materials, 4.5 percent of melamine hydrobromide, 4.25 percent of phosphonate flame retardant and 1.25 percent of flame-retardant synergist, uniformly mixing, continuously and uniformly adding the materials into a double-screw extruder by using a double-screw feeder, cooling extruded strips by a cold water tank, and cutting to obtain the product. And (3) placing the product into an oven, and then performing injection molding by using a plastic injection molding machine to obtain a standard sample strip. The injection molded bars were immediately placed in a glass desiccator at room temperature for at least 24h before performance testing. The test result shows that the flame retardant rating of the product can reach UL94V-1(3.2mm), and the yellow index (1000h) is 1.25.
Example 9
Weighing linear low-density polyethylene (the melt index MI is 17g/10min) accounting for 92% of the total weight of the materials, 3% of melamine hydrobromide, 3.75% of phosphonate flame retardant and 1.25% of flame retardant synergist, uniformly mixing, continuously and uniformly adding the materials into a double-screw extruder by using a double-screw feeder, cooling extruded strips by using a cold water tank, and cutting to obtain the product. And (3) placing the product into an oven, and then performing injection molding by using a plastic injection molding machine to obtain a standard sample strip. The injection molded bars were immediately placed in a glass desiccator at room temperature for at least 24h before performance testing. The test result shows that the flame retardant rating of the product can reach UL94V-1(3.2mm), and the yellow index (1000h) is 1.18.
Example 10
Weighing 31 percent of high-density polyethylene (the melt index MI is 20g/10min), 62 percent of linear low-density polyethylene (the melt index MI is 17g/10min), 4 percent of melamine hydrobromide, 2 percent of phosphonate flame retardant and 2 percent of flame retardant synergist by weight percent of the total weight of the materials, uniformly mixing, continuously and uniformly adding the materials into a double-screw extruder by a double-screw feeder, cooling extruded strips by a cold water tank, and then cutting the materials to obtain the product. And (3) placing the product into an oven, and then performing injection molding by using a plastic injection molding machine to obtain a standard sample strip. The injection molded bars were immediately placed in a glass desiccator at room temperature for at least 24h before performance testing. The test result shows that the flame retardant rating of the product can reach UL94V-1(3.2mm), and the yellow index (1000h) is 0.91.
Example 11
Weighing high-density polyethylene (the melt index MI is 20g/10min), low-density polyethylene (the melt index MI is 18g/10min), melamine hydrobromide 5%, phosphonate flame retardant 3% and flame retardant synergist 2% which account for 45% of the total weight of the materials, uniformly mixing, continuously and uniformly adding the materials into a double-screw extruder by using a double-screw feeder, cooling extruded strips by a cold water tank, and cutting to obtain the product. And (3) placing the product into an oven, and then performing injection molding by using a plastic injection molding machine to obtain a standard sample strip. The injection molded bars were immediately placed in a glass desiccator at room temperature for at least 24h before performance testing. The test result shows that the flame retardant rating of the product can reach UL94V-1(3.2mm), and the yellow index (1000h) is 1.13.
Example 12
Weighing low-density polyethylene (the melt index MI is 18g/10min) accounting for 30 percent of the total weight of the materials, linear low-density polyethylene (the melt index MI is 17g/10min) accounting for 61 percent of the total weight of the materials, melamine hydrobromide accounting for 3 percent, phosphonate flame retardant accounting for 4 percent and flame retardant synergist accounting for 2 percent, uniformly mixing, continuously and uniformly adding the mixture into a double-screw extruder by using a double-screw feeder, cooling extruded strips by a cold water tank, and then cutting the materials to obtain the product. And (3) placing the product into an oven, and then performing injection molding by using a plastic injection molding machine to obtain a standard sample strip. The injection molded bars were immediately placed in a glass desiccator at room temperature for at least 24h before performance testing. The test result shows that the flame retardant rating of the product can reach UL94V-1(3.2mm), and the yellow index (1000h) is 1.27.
Comparative example 1
Weighing high-density polyethylene (the melt index MI is 20g/10min) accounting for 85 percent of the total weight of the materials, 8 percent of melamine hydrobromide and 7 percent of phosphonate flame retardant, uniformly mixing, continuously and uniformly adding the materials into a double-screw extruder by using a double-screw feeder, cooling extruded strips by a cold water tank, and then cutting to obtain the product. And (3) placing the product into an oven, and then performing injection molding by using a plastic injection molding machine to obtain a standard sample strip. The injection molded bars were immediately placed in a glass desiccator at room temperature for at least 24h before performance testing. The test result shows that the flame retardant rating of the product can reach UL94V-2(3.2mm), and the yellow index (1000h) is 3.63.
It can be seen from the above comparative example 1 that when the flame retardant synergist component in the high-efficiency flame-retardant and photo-oxidation resistant polyethylene component is removed, the flame retardant effect of the product is obviously inferior to the test results in the above examples 1-12, although the flame retardant purpose can be achieved.
Comparative example 2
Weighing high-density polyethylene (the melt index MI is 20g/10min) accounting for 89% of the total weight of the materials and melamine hydrobromide 11%, uniformly mixing, continuously and uniformly adding the mixture into a double-screw extruder by using a double-screw feeder, cooling extruded strips by a cold water tank, and then cutting to obtain the product. And (3) placing the product into an oven, and then performing injection molding by using a plastic injection molding machine to obtain a standard sample strip. The injection molded bars were immediately placed in a glass desiccator at room temperature for at least 24h before performance testing. The test results showed that the product did not self-extinguish when burned vertically and the yellowness index (1000h) was 3.95.
It can be seen from the above comparative example 2 that when the flame retardant synergist and the phosphonate flame retardant component in the high-efficiency flame-retardant and anti-photooxidation polyethylene component are removed, the product cannot be self-extinguished in vertical combustion, and the purpose of flame retardance cannot be achieved.
Comparative example 3
Weighing high-density polyethylene (the melt index MI is 20g/10min) accounting for 90% of the total weight of the materials and 10% of phosphonate flame retardant, uniformly mixing, continuously and uniformly adding the mixture into a double-screw extruder by using a double-screw feeder, cooling extruded strips by using a cold water tank, and then cutting to obtain the product. And (3) placing the product into an oven, and then performing injection molding by using a plastic injection molding machine to obtain a standard sample strip. The injection molded bars were immediately placed in a glass desiccator at room temperature for at least 24h before performance testing. The test results showed that the product did not self-extinguish when burned vertically and the yellowness index (1000h) was 3.23.
It can be seen from the above comparative example 3 that when the flame retardant synergist and melamine hydrobromide component in the high-efficiency flame-retardant and anti-photooxidation polyethylene component are removed and only the phosphonate flame retardant is added, the product can not be self-extinguished in vertical combustion, and the flame retardant purpose can not be achieved.
Comparative example 4
Weighing high-density polyethylene (the melt index MI is 20g/10min) accounting for 95% of the total weight of the materials and 5% of flame-retardant synergist, uniformly mixing, continuously and uniformly adding the mixture into a double-screw extruder by using a double-screw feeder, cooling extruded strips by using a cold water tank, and then cutting to obtain the product. And (3) placing the product into an oven, and then performing injection molding by using a plastic injection molding machine to obtain a standard sample strip. The injection molded bars were immediately placed in a glass desiccator at room temperature for at least 24h before performance testing. The test results showed that the product did not self-extinguish when burned vertically and the yellowness index (1000h) was 0.53.
It can be seen from the above comparative example 4 that when the phosphonate ester flame retardant and the melamine hydrobromide component in the high-efficiency flame-retardant and anti-photooxidation polyethylene component are removed at the same time and only the flame-retardant synergist is added, the product cannot be self-extinguished in vertical combustion, and the flame-retardant purpose cannot be achieved.
It will be understood that modifications and variations can be made by persons skilled in the art in light of the above teachings and all such modifications and variations are intended to be included within the scope of the invention as defined in the appended claims.
Claims (10)
1. The high-efficiency flame-retardant photooxidation-resistant polyethylene is characterized by comprising the following components in percentage by weight: 85-95% of polyethylene, 2-8% of melamine cyanurate, 2.5-5% of phosphonate flame retardant and 0.5-2% of flame-retardant synergist.
2. The high efficiency flame retardant photooxidation resistant polyethylene of claim 1, wherein the polyethylene is one or a mixture of two or more of high density polyethylene, low density polyethylene and linear low density polyethylene.
3. The efficient flame retardant photooxidation resistant polyethylene of claim 1, wherein the melamine hydrobromide salt has the structural formula:
。
4. the efficient flame retardant and anti-photooxidation polyethylene according to claim 1, wherein the phosphonate flame retardant is 3, 9-dimethyl-3, 9-dioxo-2, 4, 8, 10-tetraoxa-3, 9-diphosphodispiro [5.5] undecane, which has the following structural formula:
。
5. the high efficiency flame retardant photooxidation resistant polyethylene according to claim 1, wherein the flame retardant synergist is an N-alkoxy hindered amine flame retardant.
6. The high efficiency flame retardant photooxidation resistant polyethylene of claim 1 wherein the polyethylene content is 88-93%.
7. The efficient flame retardant photooxidation resistant polyethylene according to claim 1, wherein the melamine cyanurate content is 3-6%.
8. The efficient flame retardant photooxidation resistant polyethylene of claim 1, wherein the phosphonate flame retardant content is 3-4%.
9. The high efficiency flame retardant photooxidation resistant polyethylene of claim 2 wherein the high density polyethylene has a melt index MI of 20g/10min and the low density polyethylene has a melt index MI of 18g/10 min.
10. The preparation method of the high-efficiency flame-retardant photooxidation-resistant polyethylene as claimed in claim 1, characterized by comprising the following steps:
A. premixing: sequentially adding polyethylene, melamine, cyanobromide, phosphonate flame retardant and flame retardant synergist into a high-speed mixer for premixing;
B. and (3) extruding and granulating: adding the premixed materials in the step A into a double-screw extruder for extrusion granulation, and cooling and granulating to obtain the required high-efficiency flame-retardant anti-photooxidation polyethylene material; wherein,
the polyethylene is one or a mixture of two or more of high-density polyethylene, low-density polyethylene and linear low-density polyethylene;
the structural formula of the melamine hydrobromide is as follows:
；
the phosphonate flame retardant is 3, 9-dimethyl-3, 9-dioxo-2, 4, 8, 10-tetraoxa-3, 9-diphosphodispiro [5.5] undecane;
the flame-retardant synergist is an N-alkoxy hindered amine flame retardant.
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| JP2018520255A (en) * | 2015-07-20 | 2018-07-26 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Flame retardant polyolefin |
| US20190010308A1 (en) * | 2015-07-20 | 2019-01-10 | Basf Se | Flame Retardant Polyolefin Articles |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2018520255A (en) * | 2015-07-20 | 2018-07-26 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Flame retardant polyolefin |
| US20190010308A1 (en) * | 2015-07-20 | 2019-01-10 | Basf Se | Flame Retardant Polyolefin Articles |
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