CN106279905A - A kind of Zero halogen flame resistance polyethylene nylon heat-shrink tube and preparation method thereof - Google Patents
A kind of Zero halogen flame resistance polyethylene nylon heat-shrink tube and preparation method thereof Download PDFInfo
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- CN106279905A CN106279905A CN201610685093.5A CN201610685093A CN106279905A CN 106279905 A CN106279905 A CN 106279905A CN 201610685093 A CN201610685093 A CN 201610685093A CN 106279905 A CN106279905 A CN 106279905A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/011—Nanostructured additives
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- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
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Abstract
The invention discloses a kind of Zero halogen flame resistance polyethylene nylon heat-shrink tube and preparation method thereof.Specifically, the Zero halogen flame resistance polyethylene nylon heat-shrink tube of the present invention comprises following component in parts by weight: polyethylene 50 ~ 80 parts, nylon 5 ~ 20 parts, block copolymer 0.5 ~ 5 part, phosphate-based flame retardant 10 ~ 30 parts, nm-class active calcium carbonate 0.5 ~ 5 part and nano silicon 0.5 ~ 5 part.Compared with prior art, the method that the Zero halogen flame resistance polyethylene nylon heat-shrink tube of the present invention utilizes physical crosslinking so that not forming covalent bond between polyethylene and nylon, molecular structure is not corrupted, it is possible to achieve follow-up recycling；The hazardous substances such as raw material is the most mercurous, cadmium, Cr VI, meet RoHS Directive requirement, harmless to environment and human body；There is good thermostability, insulating properties, anti-flammability and ideal mechanical strength, can be widely applied to various field.
Description
Technical field
The invention belongs to fire retardant thermal shrinkage tube without halogen technical field, relate to a kind of Zero halogen flame resistance polyethylene-nylon heat-shrink tube and
Its preparation method.
Background technology
The material being presently used for producing heat-shrink tube mainly includes that polyolefin based materials is (such as ethylene-vinyl acetate copolymerization
Thing), rubber type of material (such as silicone rubber), polyester material (such as polyethylene terephthalate) etc., but by above-mentioned material
Most heat-shrink tubes that material prepares are required for carrying out the complex process steps such as chemistry or crosslinking with radiation, and production cost is higher, and
And the recycling of raw material cannot be realized.Therefore, utilization has the polymeric material of physical crosslinking structure and by directly injection
The production technology of molding is prepared heat-shrink tube and is had great importance.
Summary of the invention
For above-mentioned situation, it is an object of the invention to provide a kind of Zero halogen flame resistance polyethylene-nylon heat-shrink tube and system thereof
Preparation Method, this heat-shrink tube forms physical crosslinking by nylon component, has recuperability, it is possible to realize recycling, and
The fire retardant thermal shrinkage tube without halogen of the present invention does not contains hazardness composition, will not damage environment and human body, meet European Union RoHS and refer to
Make requirement.
To achieve these goals, the present invention is by the following technical solutions:
A kind of Zero halogen flame resistance polyethylene-nylon heat-shrink tube, it comprises following component in parts by weight: polyethylene 50 ~ 80 parts, Buddhist nun
Dragon 5 ~ 20 parts, block copolymer 0.5 ~ 5 part, phosphate-based flame retardant 10 ~ 30 parts, nm-class active calcium carbonate 0.5 ~ 5 part and nanometer
Silicon dioxide 0.5 ~ 5 part；Wherein: described nylon has a general structure as shown in the formula (I):
；
Wherein: any integer that m and n is each independently in 0 ~ 4 and m+n≤4；It is arbitrary that o and p is each independently in 0 ~ 2
Integer and m+n≤2.
Preferably, described Zero halogen flame resistance polyethylene-nylon heat-shrink tube comprises following component in parts by weight: polyethylene 55
~ 75 parts, nylon 8 ~ 15 part, block copolymer 1 ~ 4 part, phosphate-based flame retardant 15 ~ 25 parts, nm-class active calcium carbonate 1 ~ 4 part and
Nano silicon 1 ~ 4 part.
It is furthermore preferred that described Zero halogen flame resistance polyethylene-nylon heat-shrink tube comprises following component in parts by weight: polyethylene
60 ~ 70 parts, nylon 10 ~ 13 parts, block copolymer 2 ~ 3 parts, phosphate-based flame retardant 15 ~ 25 parts, nm-class active calcium carbonate 2 ~ 3 parts
With nano silicon 2 ~ 3 parts.
Most preferably, described Zero halogen flame resistance polyethylene-nylon heat-shrink tube comprises following component in parts by weight: polyethylene
65 parts, nylon 12 parts, block copolymer 2.5 parts, phosphate-based flame retardant 20 parts, nm-class active calcium carbonate 2.5 parts and nanometer two
Silicon oxide 2.5 parts.
Preferably, described polyethylene is selected from linear low density polyethylene (LLDPE), Low Density Polyethylene (LDPE), highly dense
The compositions of any one or its arbitrary proportion in degree polyethylene (HDPE), preferably less than density polyethylene.
Preferably, described block copolymer selected from styrene butadiene styrene block copolymer (SBS) (SBS), styrene-
Isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), benzene second
The mixture of any one or its arbitrary proportion in alkene-ethylene-propylene, Styrene block copolymer (SEPS), preferably benzene second
Alkene-butadiene-styrene block copolymer.
Preferably, described phosphate-based flame retardant is selected from diammonium phosphate, disodium hydrogen phosphate, lithium phosphate, sodium phosphate, phosphoric acid
The mixture of any one or its arbitrary proportion in magnesium, phosphoric acid antimony, preferably phosphoric acid sodium.
Preferably, the granularity of described nm-class active calcium carbonate is 25 ~ 100 nm, preferably 30 ~ 50 nm.
Preferably, the granularity of described nano silicon is 10 ~ 50 nm, preferably 20 ~ 40 nm.
The preparation method of a kind of Zero halogen flame resistance polyethylene-nylon heat-shrink tube, it comprises the steps:
(1) weigh polyethylene, nylon, block copolymer, phosphate-based flame retardant, nm-class active calcium carbonate according to weight portion and receive
Rice silicon dioxide, and by said components mix homogeneously, obtain premix material；
(2) by the premix material of acquisition in step (1) in 180 ~ 200 DEG C of pelletizes, and on single screw extruder, tubing it is extruded into；
(3) tubing obtained in step (2) is extended 2 ~ 4 times in 150 ~ 170 DEG C, be then quenched molding, obtain halogen-free flameproof and gather
Ethylene-nylon heat-shrink tube.
Compared with prior art, the Zero halogen flame resistance polyethylene of the present invention-nylon heat-shrink tube has the advantage that
(1) method utilizing physical crosslinking so that not forming covalent bond between polyethylene and nylon, molecular structure is broken
Bad, it is possible to achieve follow-up recycling；
(2) hazardous substances such as raw material the most mercurous, cadmium, Cr VI, meets RoHS Directive requirement；
(3) without halogen and red phosphorus in fire retardant, noxious substance will not after burning, be produced, harmless to environment and human body；
(4) there is good thermostability, insulating properties, anti-flammability and ideal mechanical strength, can be widely applied to various
Field.
Detailed description of the invention
Example below will be further illustrated the present invention.These embodiments are merely to illustrate the present invention, but not to appoint
Where formula limits the present invention.
Embodiment 1: Zero halogen flame resistance polyethylene-nylon heat-shrink tube.
Weigh Low Density Polyethylene 50 kg, nylon () 5 kg, benzene
Ethylene-butadiene-styrene block copolymer 0.5 kg, sodium phosphate 10 kg, nm-class active calcium carbonate (granularity is 25 nm) 0.5
Kg and nano silicon (granularity is 10 nm) 0.5 kg, and by said components mix homogeneously, obtain premix material；
(2) by the premix material of acquisition in step (1) in 200 DEG C of pelletizes, and on single screw extruder, tubing it is extruded into；
(3) tubing obtained in step (2) is extended 2 times in 170 DEG C, be then quenched molding, obtain Zero halogen flame resistance polyethylene-Buddhist nun
Dragon heat-shrink tube.
Embodiment 2: Zero halogen flame resistance polyethylene-nylon heat-shrink tube.
Weigh Low Density Polyethylene 80 kg, nylon (
) 20 kg, styrene butadiene styrene block copolymer (SBS) 5 kg, sodium phosphate 30 kg, (granularity is nm-class active calcium carbonate
100 nm) 5 kg and nano silicon (granularity is 50 nm) 5 kg, and by said components mix homogeneously, obtain premix material；
(2) by the premix material of acquisition in step (1) in 200 DEG C of pelletizes, and on single screw extruder, tubing it is extruded into；
(3) tubing obtained in step (2) is extended 2 times in 170 DEG C, be then quenched molding, obtain Zero halogen flame resistance polyethylene-Buddhist nun
Dragon heat-shrink tube.
Embodiment 3: Zero halogen flame resistance polyethylene-nylon heat-shrink tube.
Weigh Low Density Polyethylene 55 kg, nylon (
) 8 kg, styrene butadiene styrene block copolymer (SBS) 1 kg, sodium phosphate 15 kg, (granularity is 30 to nm-class active calcium carbonate
Nm) 1 kg and nano silicon (granularity is 20 nm) 1 kg, and by said components mix homogeneously, obtain premix material；
(2) by the premix material of acquisition in step (1) in 200 DEG C of pelletizes, and on single screw extruder, tubing it is extruded into；
(3) tubing obtained in step (2) is extended 2 times in 150 DEG C, be then quenched molding, obtain Zero halogen flame resistance polyethylene-Buddhist nun
Dragon heat-shrink tube.
Embodiment 4: Zero halogen flame resistance polyethylene-nylon heat-shrink tube.
Weigh Low Density Polyethylene 60 kg, nylon () 10
Kg, styrene butadiene styrene block copolymer (SBS) 2 kg, sodium phosphate 15 kg, nm-class active calcium carbonate (granularity is 50 nm)
2 kg and nano silicon (granularity is 40 nm) 2 kg, and by said components mix homogeneously, obtain premix material；
(2) by the premix material of acquisition in step (1) in 200 DEG C of pelletizes, and on single screw extruder, tubing it is extruded into；
(3) tubing obtained in step (2) is extended 2 times in 150 DEG C, be then quenched molding, obtain Zero halogen flame resistance polyethylene-Buddhist nun
Dragon heat-shrink tube.
Embodiment 5: Zero halogen flame resistance polyethylene-nylon heat-shrink tube.
Weigh Low Density Polyethylene 65 kg, nylon () 12
(granularity is 40 for kg, styrene butadiene styrene block copolymer (SBS) 2.5 kg, sodium phosphate 20 kg, nm-class active calcium carbonate
Nm) 2.5 kg and nano silicon (granularity is 30 nm) 2.5 kg, and by said components mix homogeneously, obtain premix material；
(2) by the premix material of acquisition in step (1) in 200 DEG C of pelletizes, and on single screw extruder, tubing it is extruded into；
(3) tubing obtained in step (2) is extended 2 times in 150 DEG C, be then quenched molding, obtain Zero halogen flame resistance polyethylene-Buddhist nun
Dragon heat-shrink tube.
Embodiment 6: Zero halogen flame resistance polyethylene-nylon heat-shrink tube performance test.
Zero halogen flame resistance polyethylene-nylon the heat-shrink tube obtained in embodiment 1 to 5 is carried out performance test, its result such as table 1
Shown in.
Table 1. Zero halogen flame resistance polyethylenes-nylon heat-shrink tube performance test
As seen from the above table, the hazardous substances such as the Zero halogen flame resistance polyethylene of the present invention-nylon heat-shrink tube is the most mercurous, cadmium, Cr VI,
Meet RoHS Directive requirement；Without halogen and red phosphorus, noxious substance after burning, will not be produced, harmless to environment and human body；
There is good thermostability, insulating properties, anti-flammability and ideal mechanical strength.
The aforementioned description to the specific illustrative embodiment of the present invention illustrates that and the purpose of illustration.These describe not
Think the limit present invention, or limit the invention to disclosed precise forms；On the contrary, according to above-mentioned teaching, can carry out very
Many changes and change.The purpose selected exemplary embodiment and describe is to explain the certain principles and in fact of the present invention
Border is applied, so that others skilled in the art are capable of and utilize the various different exemplary enforcement of the present invention
Scheme and various different selection and change.The scope of the present invention is intended to by appending claims and equivalents institute thereof
Limit.
Claims (10)
1. Zero halogen flame resistance polyethylene-nylon heat-shrink tube, it comprises following component in parts by weight: polyethylene 50 ~ 80 parts,
Nylon 5 ~ 20 parts, block copolymer 0.5 ~ 5 part, phosphate-based flame retardant 10 ~ 30 parts, nm-class active calcium carbonate 0.5 ~ 5 part and receive
Rice silicon dioxide 0.5 ~ 5 part；Wherein: described nylon has a general structure as shown in the formula (I):
；
Wherein: any integer that m and n is each independently in 0 ~ 4 and m+n≤4；It is arbitrary that o and p is each independently in 0 ~ 2
Integer and m+n≤2.
Zero halogen flame resistance polyethylene the most according to claim 1-nylon heat-shrink tube, it is characterised in that it comprises with weight portion
Meter following component: polyethylene 55 ~ 75 parts, nylon 8 ~ 15 part, block copolymer 1 ~ 4 part, phosphate-based flame retardant 15 ~ 25 parts,
Nm-class active calcium carbonate 1 ~ 4 part and nano silicon 1 ~ 4 part.
Zero halogen flame resistance polyethylene the most according to claim 2-nylon heat-shrink tube, it is characterised in that it comprises with weight portion
Meter following component: polyethylene 60 ~ 70 parts, nylon 10 ~ 13 parts, block copolymer 2 ~ 3 parts, phosphate-based flame retardant 15 ~ 25 parts,
Nm-class active calcium carbonate 2 ~ 3 parts and nano silicon 2 ~ 3 parts.
Zero halogen flame resistance polyethylene the most according to claim 2-nylon heat-shrink tube, it is characterised in that it comprises with weight portion
The following component of meter: polyethylene 65 parts, nylon 12 parts, block copolymer 2.5 parts, phosphate-based flame retardant 20 parts, nano active
Calcium carbonate 2.5 parts and nano silicon 2.5 parts.
Zero halogen flame resistance polyethylene the most according to any one of claim 1 to 4-nylon heat-shrink tube, it is characterised in that described
The polyethylene any one or its arbitrary proportion in linear low density polyethylene, Low Density Polyethylene, the high density polyethylene (HDPE)
Compositions.
Zero halogen flame resistance polyethylene the most according to any one of claim 1 to 4-nylon heat-shrink tube, it is characterised in that described
Block copolymer is selected from styrene butadiene styrene block copolymer (SBS), styrene-isoprene-phenylethene block copolymerization
Appointing in thing, styrene-ethylene-butylene-styrene block copolymer, styrene ethylene-propylene-styrene block copolymer
Anticipate a kind of or mixture of its arbitrary proportion.
Zero halogen flame resistance polyethylene the most according to any one of claim 1 to 4-nylon heat-shrink tube, it is characterised in that described
It is any one that phosphate-based flame retardant is selected from diammonium phosphate, disodium hydrogen phosphate, lithium phosphate, sodium phosphate, magnesium phosphate, phosphoric acid antimony
Plant or the mixture of its arbitrary proportion.
Zero halogen flame resistance polyethylene the most according to any one of claim 1 to 4-nylon heat-shrink tube, it is characterised in that described
The granularity of nm-class active calcium carbonate is 25 ~ 100 nm.
Zero halogen flame resistance polyethylene the most according to any one of claim 1 to 4-nylon heat-shrink tube, it is characterised in that described
The granularity of nano silicon is 10 ~ 50 nm.
10. a preparation method for the Zero halogen flame resistance polyethylene according to any one of claim 1 to 9-nylon heat-shrink tube, its bag
Include following steps:
1) weigh polyethylene, nylon, block copolymer, phosphate-based flame retardant, nm-class active calcium carbonate according to weight portion and receive
Rice silicon dioxide, and by said components mix homogeneously, obtain premix material；
2) by the premix material that obtains in step 1) in 180 ~ 200 DEG C of pelletizes, and on single screw extruder, tubing it is extruded into；
3) by step 2) in obtain tubing in 150 ~ 170 DEG C extend 2 ~ 4 times, be then quenched molding, obtain the poly-second of halogen-free flameproof
Alkene-nylon heat-shrink tube.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106750825A (en) * | 2017-01-20 | 2017-05-31 | 成都新硕新材料有限公司 | A kind of resistance to 125 DEG C of halogen-free flame-retardant composite materials and its preparation method and application |
| WO2020152974A1 (en) * | 2019-01-22 | 2020-07-30 | 三菱瓦斯化学株式会社 | Polyamide resin, composition, and molded article |
| JP2020117588A (en) * | 2019-01-22 | 2020-08-06 | 三菱瓦斯化学株式会社 | Polyamide resin, composition and molded article |
| CN112480518A (en) * | 2020-12-10 | 2021-03-12 | 安徽理工大学 | Formula of modified detonating tube |
| WO2021241471A1 (en) * | 2020-05-29 | 2021-12-02 | 三菱瓦斯化学株式会社 | Polyamide resin, polyamide resin composition and molded article |
| JP7021725B1 (en) * | 2020-08-20 | 2022-02-17 | 三菱瓦斯化学株式会社 | Polyamide resin |
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| EP4159790A4 (en) * | 2020-05-29 | 2023-11-22 | Mitsubishi Gas Chemical Company, Inc. | Polyamide resin, polyamide resin composition, and molded product |
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| WO2022038865A1 (en) * | 2020-08-20 | 2022-02-24 | 三菱瓦斯化学株式会社 | Polyamide resin |
| JP7021724B1 (en) * | 2020-08-20 | 2022-02-17 | 三菱瓦斯化学株式会社 | Polyamide resin |
| KR20230038815A (en) * | 2020-08-20 | 2023-03-21 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | polyamide resin |
| EP4201978A4 (en) * | 2020-08-20 | 2024-02-14 | Mitsubishi Gas Chemical Co | Polyamide resin |
| CN112480518A (en) * | 2020-12-10 | 2021-03-12 | 安徽理工大学 | Formula of modified detonating tube |
| WO2023089941A1 (en) * | 2021-11-18 | 2023-05-25 | 三菱瓦斯化学株式会社 | Method for manufacturing polyamide resin, and resin composition |
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Application publication date: 20170104 |