CN106496758A - A kind of three generations's nuclear power halogen-free non-red-phosphorus flame-retardant thermal shrinkable tube and preparation method thereof - Google Patents
A kind of three generations's nuclear power halogen-free non-red-phosphorus flame-retardant thermal shrinkable tube and preparation method thereof Download PDFInfo
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- CN106496758A CN106496758A CN201610977703.9A CN201610977703A CN106496758A CN 106496758 A CN106496758 A CN 106496758A CN 201610977703 A CN201610977703 A CN 201610977703A CN 106496758 A CN106496758 A CN 106496758A
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
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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
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0866—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
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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
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0866—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation
- B29C2035/0877—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation using electron radiation, e.g. beta-rays
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2023/00—Tubular articles
- B29L2023/22—Tubes or pipes, i.e. rigid
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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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
- C08L2312/06—Crosslinking by radiation
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Abstract
A kind of three generations's nuclear power halogen-free non-red-phosphorus flame-retardant thermal shrinkable tube, is grouped into by following group in parts by weight：100 parts of ethylene methyl acrylate copolymer；APP 80-110 parts；Composite light stabilizer 1-2 parts；Compound ultra-violet absorber 1-2 parts；Composite antioxidant 4-6 parts；The degree of polymerization of the APP is more than 1000, and is coated by melamine, Firebrake ZB twice；The composite light stabilizer is light stabilizer 944 with light stabilizer 770 according to 1:1 ratio mixture is formed；Described compound ultra-violet absorber is ultra-violet absorber UV329 and ultra-violet absorber UV531 according to 1:1 ratio mixture is formed；The composite antioxidant is antioxidant 1076, irgasfos 168 and anti-oxidant DLTP according to 2:1：1 ratio mixture is formed.Heat-shrink tube halogen-free flameproof of the present invention, 90 DEG C can use 65 years, and tolerate the dose of radiation of 2600kGy and tested by LOCA.
Description
Technical field
The present invention relates to a kind of used in nuclear power station heat-shrink tube.
Background technology
CAP1400 and No. Hua Longyi, be the Typical Representative of three generations's nuclear power technology.
Three generations's nuclear power technology requires nuclear power heat-shrink tube halogen-free flameproof, and 90 DEG C can use 65 years, and tolerate 2600kGy's
Dose of radiation and tested by LOCA.
The country does not meet the pyrocondensation Manifold technology of three generations's nuclear power technology requirement nuclear power, the whole imports of product at present.
Content of the invention
The technical problem to be solved in the present invention is：A kind of nuclear power pyrocondensation for meeting three generations's nuclear power technology requirement is provided
Pipe, the heat-shrink tube halogen-free flameproof, 90 DEG C can use 65 years, and tolerate the dose of radiation of 2600kGy and tested by LOCA.
In order to solve above-mentioned technical problem, the present invention proposes following technical proposal：A kind of three generations's nuclear power Halogen no red phosphorus
Fire retardant thermal shrinkage tube, is grouped into by following group in parts by weight：100 parts of ethylene-methyl acrylate copolymer；APP
80-110 parts；Composite light stabilizer 1-2 parts；Compound ultra-violet absorber 1-2 parts；Composite antioxidant 4-6 parts；
The degree of polymerization of the APP is more than 1000, and is coated by melamine, Firebrake ZB twice；
The composite light stabilizer is poly- { [6- [(1,1,3,3- tetramethyl butyls) amino]] -1,3,5- triazines -2,4- pair
[(2,2,6,6,-tetramethyl-4-piperidyl) imino group] -1,6- hexamethylene diamines [(2,2,6,6- tetramethyl -4- piperidyls) imino group] }
With bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate according to 1:1 ratio mixture is formed；
Described compound ultra-violet absorber be 2- (2 '-hydroxyl -3 ', 5 '-t-octyl phenyl) BTA with 2- hydroxyls -
4- oxy-octyl benzophenones are according to 1:1 ratio mixture is formed；
The composite antioxidant is β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid, three [2.4- bis-
Tert-butyl-phenyl] the double lauryls of phosphite ester and thio-2 acid are according to 2：1：1 ratio mixture is formed.
In order to solve above-mentioned technical problem, the present invention also proposes following technical proposal：A kind of three generations's nuclear power Halogen is without red
The preparation method of phosphorus fire retardant thermal shrinkage tube, takes 100 parts of ethylene-methyl acrylate copolymer by weight；APP 80-110
Part；Composite light stabilizer 1-2 parts；Compound ultra-violet absorber 1-2 parts；Composite antioxidant 4-6 parts；Through banbury and double
Screw extruder mixing granulator, is then extruded into tubing with single screw extrusion machine, and the tubing accelerates through Co 60 or electronics
Device 130-150KGy crosslinkings with radiation, the tubing after crosslinking with radiation expand 3-6 times at a temperature of 120-140 DEG C.
Compared with prior art, the present invention has following beneficial effect：
1st, a kind of nuclear power heat-shrink tube for meeting three generations's nuclear power technology requirement of present invention offer, the heat-shrink tube halogen-free flameproof,
Can be tested by VW-1,90 DEG C can use 65 years, and tolerate the dose of radiation of 2600kGy and tested by LOCA.Peace
Be mounted in containment, which can be completed under ambient environment, under earthquake load and under accident environment and after accident
Predetermined function.
2nd, APP easily absorbs water, and after water suction, reduces its flame retardant effect, it is impossible to test by VW--1, in addition also without
The online lettering of method.From APP of the degree of polymerization more than 1000, first coated with melamine, then coated with Firebrake ZB, coated twice
After, polyphosphoric acid is completely in the middle of melamine and Firebrake ZB, is coated solid and reliable, the heat-shrink tube good flame resistance of preparation, can be passed through
VW--1 is tested, and realizes online lettering.
3rd, light stabilizer 944, light stabilizer 770 are made with ultra-violet absorber UV329, ultra-violet absorber UV531 synergistics
With obvious, the radiation resistance of material is significantly improved, be resistant to the dose of radiation of 2600kGy.
4th, antioxidant 1076, irgasfos 168 and anti-oxidant DLTP are according to 2:1：1 ratio mixture, with significant synergistic
Effect, material can 90 DEG C can use 65 years.
Specific embodiment
The present invention proposes a kind of three generations's nuclear power halogen-free non-red-phosphorus flame-retardant thermal shrinkable tube, by following group in parts by weight
It is grouped into：100 parts of ethylene-methyl acrylate copolymer；APP 80-110 parts；Composite light stabilizer 1-2 parts；Compound purple
Ultraviolet absorbers 1-2 parts；Composite antioxidant 4-6 parts.
The degree of polymerization of the APP is more than 1000, and is coated by melamine, Firebrake ZB twice.
The composite light stabilizer is poly- { [6- [(1,1,3,3- tetramethyl butyls) amino]] -1,3,5- triazines -2,4- pair
[(2,2,6,6,-tetramethyl-4-piperidyl) imino group] -1,6- hexamethylene diamines [(2,2,6,6- tetramethyl -4- piperidyls) imino group] }
(light stabilizer 944) and bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate (light stabilizer 770) are according to 1:1 ratio
Mixture is formed.
Described compound ultra-violet absorber is that 2- (2 '-hydroxyl -3 ', 5 '-t-octyl phenyl) BTA (inhale by ultraviolet
Receive agent UV329) with UV-531 (ultra-violet absorber UV531) according to 1:1 ratio mixture is formed.
The composite antioxidant is β-positive octadecanol ester (antioxidant of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid
1076), three [2.4- di-tert-butyl-phenyls] phosphite ester (irgasfos 168) and the double lauryl (antioxidant of thio-2 acid
DLTP) according to 2：1：1 ratio mixture is formed.
The preparation method of above-mentioned three generations's nuclear power halogen-free non-red-phosphorus flame-retardant thermal shrinkable tube, comprises the steps：
Step one：Ethylene-methyl acrylate copolymer 100 part is taken by weight；APP 80-110 parts；Compound
Light stabilizer 1-2 parts；Compound ultra-violet absorber 1-2 parts；Composite antioxidant 4-6 parts；
Step 2：Through banbury and double screw extruder mixing granulator, then tubing is extruded into single screw extrusion machine,
, through Co 60 or electron accelerator 130-150KGy crosslinkings with radiation, the tubing after crosslinking with radiation is at 120-140 DEG C for the tubing
At a temperature of expand 3-6 times.
Prepare embodiment 1
Ethylene-methyl acrylate copolymer 100 part is taken by weight；80 parts of APP；1 part of composite light stabilizer；
1 part of compound ultra-violet absorber；4 parts of composite antioxidant.
Then above material is extruded into pipe with single screw extrusion machine through banbury and double screw extruder mixing granulator
Material, through electron accelerator 130KGy crosslinkings with radiation, the tubing after crosslinking with radiation expands 3 times at a temperature of 120 DEG C to the tubing,
Obtain three generations's nuclear power halogen-free non-red-phosphorus flame-retardant thermal shrinkable tube, its performance such as table 1.
Prepare embodiment 2
Ethylene-methyl acrylate copolymer 100 part is taken by weight；110 parts of APP；2 parts of composite light stabilizer；
2 parts of compound ultra-violet absorber；6 parts of composite antioxidant.
Then above material is extruded into pipe with single screw extrusion machine through banbury and double screw extruder mixing granulator
Material, through electron accelerator 150KGy crosslinkings with radiation, the tubing after crosslinking with radiation expands 6 times at a temperature of 140 DEG C to the tubing,
Obtain three generations's nuclear power halogen-free non-red-phosphorus flame-retardant thermal shrinkable tube, its performance such as table 1.
Prepare embodiment 3
Ethylene-methyl acrylate copolymer 100 part is taken by weight；95 parts of APP；Composite light stabilizer 1.5
Part；1.5 parts of compound ultra-violet absorber；5 parts of composite antioxidant.
Then above material is extruded into pipe with single screw extrusion machine through banbury and double screw extruder mixing granulator
Material, through Co 60 or electron accelerator 140KGy crosslinkings with radiation, the tubing after crosslinking with radiation is at a temperature of 130 DEG C for the tubing
5 times of expansion, obtains three generations's nuclear power halogen-free non-red-phosphorus flame-retardant thermal shrinkable tube, its performance such as table 1.
Comparative example 1
Ethylene-methyl acrylate copolymer 100 part is taken by weight；80 parts of APP；1 part of composite light stabilizer；
1 part of compound ultra-violet absorber；4 parts of composite antioxidant.Wherein APP is only coated once with Firebrake ZB.
Then above material is extruded into pipe with single screw extrusion machine through banbury and double screw extruder mixing granulator
Material, through electron accelerator 130KGy crosslinkings with radiation, the tubing after crosslinking with radiation expands 3 times at a temperature of 120 DEG C to the tubing,
Obtain three generations's nuclear power halogen-free non-red-phosphorus flame-retardant thermal shrinkable tube, its performance such as table 1.
Comparative example 2
Ethylene-methyl acrylate copolymer 100 part is taken by weight；80 parts of APP；1 part of composite light stabilizer；
1 part of compound ultra-violet absorber；4 parts of composite antioxidant.Wherein APP is only coated once with melamine.
Then above material is extruded into pipe with single screw extrusion machine through banbury and double screw extruder mixing granulator
Material, through electron accelerator 130KGy crosslinkings with radiation, the tubing after crosslinking with radiation expands 3 times at a temperature of 120 DEG C to the tubing,
Obtain three generations's nuclear power halogen-free non-red-phosphorus flame-retardant thermal shrinkable tube, its performance such as table 1.
Comparative example 3
Ethylene-methyl acrylate copolymer 100 part is taken by weight；80 parts of APP；1 part of composite light stabilizer；
1 part of compound ultra-violet absorber；4 parts of composite antioxidant.Wherein APP Firebrake ZB, melamine cladding are secondary twice.
Then above material is extruded into pipe with single screw extrusion machine through banbury and double screw extruder mixing granulator
Material, through electron accelerator 130KGy crosslinkings with radiation, the tubing after crosslinking with radiation expands 3 times at a temperature of 120 DEG C to the tubing,
Obtain three generations's nuclear power halogen-free non-red-phosphorus flame-retardant thermal shrinkable tube, its performance such as table 1.
Comparative example 4
Ethylene-methyl acrylate copolymer 100 part is taken by weight；110 parts of APP；944 2 parts of light stabilizer；
2 parts of compound ultra-violet absorber；6 parts of composite antioxidant.
Then above material is extruded into pipe with single screw extrusion machine through banbury and double screw extruder mixing granulator
Material, through electron accelerator 150KGy crosslinkings with radiation, the tubing after crosslinking with radiation expands 6 times at a temperature of 140 DEG C to the tubing,
Obtain three generations's nuclear power halogen-free non-red-phosphorus flame-retardant thermal shrinkable tube, its performance such as table 1.
Comparative example 5
Ethylene-methyl acrylate copolymer 100 part is taken by weight；95 parts of APP；Composite light stabilizer 1.5
Part；2 parts of ultra-violet absorber UV329；5 parts of composite antioxidant.
Then above material is extruded into pipe with single screw extrusion machine through banbury and double screw extruder mixing granulator
Material, through Co 60 or electron accelerator 140KGy crosslinkings with radiation, the tubing after crosslinking with radiation is at a temperature of 130 DEG C for the tubing
5 times of expansion, obtains three generations's nuclear power halogen-free non-red-phosphorus flame-retardant thermal shrinkable tube, its performance such as table 1.
Comparative example 6
Ethylene-methyl acrylate copolymer 100 part is taken by weight；95 parts of APP；1.5 parts of composite light stabilizer；Multiple
Close 2 parts of ultra-violet absorber；Antioxidant 1076 and irgasfos 168 are according to 2:15 parts of ratio mixture.
Then above material is extruded into pipe with single screw extrusion machine through banbury and double screw extruder mixing granulator
Material, through Co 60 or electron accelerator 140KGy crosslinkings with radiation, the tubing after crosslinking with radiation is at a temperature of 130 DEG C for the tubing
5 times of expansion, obtains three generations's nuclear power halogen-free non-red-phosphorus flame-retardant thermal shrinkable tube, its performance such as table 1.
Table 1：Heat-shrink tube physical and chemical performance of the present invention
As can be seen from Table 1, the cladding of APP is extremely important, is only coated once with Firebrake ZB or melamine, fire-retardant
Can not be tested by vw--1, with Firebrake ZB cladding once after again with melamine coat once, fire-retardant can not be tested by vw--1,
Only with melamine cladding once after, then coated once with Firebrake ZB, fire-retardant could be tested by vw--1.
Claims (2)
1. a kind of three generations's nuclear power halogen-free non-red-phosphorus flame-retardant thermal shrinkable tube, is grouped into by following group in parts by weight：Ethene-
100 parts of methyl acrylate copolymer；APP 80-110 parts；Composite light stabilizer 1-2 parts；Compound ultra-violet absorber
1-2 parts；Composite antioxidant 4-6 parts；
The degree of polymerization of the APP is more than 1000, and is coated by melamine, Firebrake ZB twice；
The composite light stabilizer is poly- { [6- [(1,1,3,3- tetramethyl butyls) amino]] -1,3,5- triazines -2,4- pair
[(2,2,6,6,-tetramethyl-4-piperidyl) imino group] -1,6- hexamethylene diamines [(2,2,6,6- tetramethyl -4- piperidyls) imino group] }
With double (2,2,6,6--4-piperidyls of tetramethyl) sebacates according to 1:1 ratio mixture is formed；
Described compound ultra-violet absorber is 2-（2 '-hydroxyl -3 ', 5 '-t-octyl phenyl）BTA is with 2- hydroxyls -4- just
Octyloxybenzophenone is according to 1:1 ratio mixture is formed；
The composite antioxidant be β-（3,5- di-tert-butyl-hydroxy phenyls）The positive octadecanol ester of propionic acid, three [bis- tertiary fourths of 2.4-
Base phenyl] the double lauryls of phosphite ester and thio-2 acid are according to 2：1：1 ratio mixture is formed.
2. the preparation method of a kind of three generations's nuclear power halogen-free non-red-phosphorus flame-retardant thermal shrinkable tube according to claim 1, its feature
It is：Ethylene-methyl acrylate copolymer 100 part is taken by weight；APP 80-110 parts；Composite light stabilizer 1-
2 parts；Compound ultra-violet absorber 1-2 parts；Composite antioxidant 4-6 parts；
Through banbury and double screw extruder mixing granulator, then tubing is extruded into single screw extrusion machine, the tubing warp
Co 60 or electron accelerator 130-150KGy crosslinkings with radiation is crossed, the tubing after crosslinking with radiation is expanded at a temperature of 120-140 DEG C
3-6 times.
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| CN201610977703.9A CN106496758B (en) | 2016-11-08 | 2016-11-08 | A kind of three generations's nuclear power halogen-free non-red-phosphorus flame-retardant thermal shrinkable tube and preparation method thereof |
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| 吕建平 等: ""密胺树脂/硼酸锌双层包覆微胶囊化红磷的制备及其在阻燃聚烯烃中的应用"", 《功能高分子学报》 * |
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| Publication number | Publication date |
|---|---|
| CN106496758B (en) | 2019-01-29 |
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