CN109679143A - Flame retardant microcapsule and the silicane crosslinking flame retardant polyolefin cable material with low smoke halogen being prepared by it - Google Patents
Flame retardant microcapsule and the silicane crosslinking flame retardant polyolefin cable material with low smoke halogen being prepared by it Download PDFInfo
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- CN109679143A CN109679143A CN201811638736.6A CN201811638736A CN109679143A CN 109679143 A CN109679143 A CN 109679143A CN 201811638736 A CN201811638736 A CN 201811638736A CN 109679143 A CN109679143 A CN 109679143A
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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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
- C08L2201/22—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
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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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
- C08L2312/08—Crosslinking by silane
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Abstract
The present invention provides flame retardant microcapsule, silicane crosslinking flame retardant polyolefin cable material with low smoke halogen and preparation method containing the flame retardant microcapsule.For the present invention using inorganic fire retardants as capsule-core, selection rubber is capsule material, and the microencapsulation for carrying out physics cladding to fire retardant is handled, and prepares silicane crosslinking flame retardant polyolefin cable material with low smoke halogen using the microcapsules.Microcapsules processing is carried out to fire retardant using physics cladding process, is not related to polymerization reaction in treatment process, cladding process is not influenced by complicated factors such as reaction conditions, covered effect temperature-controllable, and operating procedure is simple.Flame retardant microcapsule of the invention has improved dispersibility and compatibility, and can improve the processing performance of silane cross-linked polyolefin cable material.
Description
Technical field
The invention belongs to fire retardants and fire proofing field, and in particular to a kind of fire retardant of rubber coated inorganic fire retardants
Microcapsules and preparation method thereof and a kind of silane crosslinked halogen-free flame-retardant cable material of polyolefin containing the flame retardant microcapsule and
Preparation method.
Background technique
To reduce fire caused by wire and cable aging and overload use etc., flame-retardant electric wire and cable usage amount is more and more,
And low-smoke halogen-free flame-retardant electric wire and cable makes fire-resistant wire from now on due to having the superior performance such as environmental protection, low cigarette, fire-retardant
The hot and difficult issue of field of cables.
Polyethylene crosslinking is broadly divided into physical crosslinking and chemical crosslinking two major classes.Physical crosslinking also referred to as cross-linking radiation, one
As be suitable for the relatively thin low-voltage cable of insulation thickness, and there are investments it is big, inconvenient the disadvantages of.General point of chemical crosslinking
For peroxide crosslinking and two kinds of silane grafting and crosslinking.Chemical Crosslinking Methods are simpler than irradiation crosslinking processes, safe operation.Peroxide
There is also some disadvantages for compound crosslinked polyethylene: process is difficult to control, and is easy to appear premature cure phenomenon；Crosslinking is molten
Point or fusing point nearby occur, and polyethylene is easy softening transform, need continuous solidification equipment after molding, complex technical process.
Patent in relation to crosslinked with silicane fireproofing cable material without halide has a kind of Halogen of crosslinked with silicane of CN103013021A
The preparation method and CN1923879A silicane crosslinking flame retardant polyolefin cable material with low smoke halogen of flame-proof polyolefine cable material and its life
Production. art.What is introduced in CN103013021A is a kind of to open with improved polyolefin cable preparation method for material, environmental stress resistance
Fragility can be with the halogen-free flameproof of fire retardant dispersibility, the crosslinked with silicane for being suitble to the production flexible cables such as electric wire and transmission line class product
Cable material of polyolefin.What is introduced in CN1923879A is a kind of silicane crosslinking flame retardant polyolefin cable material with low smoke halogen of two step method
And its production technology.
Traditional two-step method manufacture silicane crosslinking flame retardant polyolefin cable material with low smoke halogen has the disadvantage that raw material are squeezing
Out in the polypropylene fusion graft process of machine, fire retardant solid powder causes material fluidity poor, and twin-screw shearing friction heat is serious.Temperature
Spending height can be such that side reaction aggravates, and squeeze out difficult, easily cause grafting melt premature cure crosslinking, caused by loss it is huge.
Therefore, the dispersibility with improvement that there is still a need for a kind of for this field and compatibility and crosslinked with silicane polyene can be improved
The fire retardant of the processing performance of hydrocarbon CABLE MATERIALS and a kind of crosslinked with silicane low-smoke non-halogen flame-retardant with improved processing performance are poly-
Alkene CABLE MATERIALS.
Summary of the invention
The first object of the present invention is to overcome the above silicane crosslinking flame retardant polyolefin cable material with low smoke halogen preparation skill
Problem and shortage existing for art improves the processing performance in extrusion process, provides a kind of Liquid Ethylene Propylene Methylene cladded aluminium hydroxide
Flame retardant microcapsule and preparation method thereof.
The second object of the present invention is to obtain a kind of crosslinked with silicane low-smoke non-halogen flame-retardant with improved processing performance
Composition of cable material of polyolefin and preparation method thereof.
The third object of the present invention is to obtain a kind of crosslinked with silicane low-smoke non-halogen flame-retardant with improved processing performance
Cable material of polyolefin and preparation method thereof.
Specifically, the present invention provides a kind of flame retardant microcapsule, the flame retardant microcapsule is the inorganic of rubber coated
Fire retardant.
In one or more embodiments, the rubber is Liquid Ethylene Propylene Methylene, butyl rubber or combinations thereof；It is preferred that
Ground, the Liquid Ethylene Propylene Methylene are selected from liquid ethylene-propylene-diene rubber, liquid dihydric EP rubbers or combinations thereof.
In one or more embodiments, the rubber is liquid ethylene-propylene-diene rubber.
In one or more embodiments, the inorganic fire retardants is selected from aluminium hydroxide, magnesium hydroxide or combinations thereof；It is excellent
It is selected as aluminium hydroxide.
In one or more embodiments, the weight ratio of the rubber and inorganic fire retardants is 10-50:100, preferably
20-40:100, more preferably 30-40:100.
In one or more embodiments, average grain diameter≤800 mesh of the inorganic fire retardants, preferably in 1000-
In the range of 5000 mesh.
In one or more embodiments, the flame retardant microcapsule is the hydroxide of liquid ethylene-propylene-diene rubber cladding
Aluminium, wherein the weight ratio of liquid ethylene-propylene-diene rubber and aluminium hydroxide is 30-40:100.
The present invention also provides the methods for preparing flame retardant microcapsule of the present invention, and the method includes stirring inorganic resistance
The mixture of agent and rubber is fired, thus to obtain the flame retardant microcapsule.
The present invention also provides the flame retardant microcapsules being prepared using the method for the invention.
The present invention also provides a kind of crosslinked with silicane containing flame retardant microcapsule described in any embodiment of the present invention is low
The composition of cigarette phosphorus flame retardant etc., the composition contain the following parts by weight:
In one or more embodiments, the composition is the particle that acquisition is squeezed out at a temperature of 100-150 DEG C；It is excellent
Choosing, it is described to be extruded as squeezing out using reciprocating single-bolt extruder.
The present invention also provides a kind of crosslinked with silicane containing flame retardant microcapsule described in any embodiment of the present invention is low
Cigarette phosphorus flame retardant etc., the cable material of polyolefin include that A material and B expect,
The A material contains the following parts by weight:
The B material contains the following parts by weight:
In one or more embodiments, in the cable material of polyolefin, A material and the weight ratio of B material are (90-99):
(1-10)。
In one or more embodiments, in the A material, the dosage of the flame retardant microcapsule is 50-80 parts by weight,
And the weight ratio of rubber and inorganic fire retardants is 30-40:100 in flame retardant microcapsule and A material with the B weight ratio expected is
(93-97): (3-7).
The present invention also provides a kind of sides for preparing silicane crosslinking flame retardant polyolefin cable material with low smoke halogen of the present invention
Method, described method includes following steps:
Each component of A material and B material is provided；
It mixes A and expects each component, and squeezed out in 100-150 DEG C, is granulated, obtain A material particulate material；Preferably, described to be extruded as
It is squeezed out using reciprocating single-bolt extruder；
It mixes B and expects each component, and be kneaded in 140-190 DEG C, is granulated, obtain B material particulate material；With
The A material particulate material and B material particulate material are mixed, is squeezed out at 140-190 DEG C；
Thus the phosphorus flame retardant etc. of crosslinked with silicane is obtained.
In one or more embodiments, the A material particulate material and B material particulate material are according to (90-99): the weight of (1-10)
The mixing of amount ratio.
The present invention also provides the crosslinked with silicane low smoke halogen-free flame-retardant polyolefins being prepared using method of the present invention
CABLE MATERIALS.
Specific embodiment
To make those skilled in the art can be appreciated that the features of the present invention and effect, below sincerely with regard to specification and claims
In the term that refers to and term carry out general explanation and definition.Unless otherwise specified, otherwise all technologies used herein
And scientific words, it is that those skilled in the art answer the ordinary meaning of the invention understood when there is collision scenario
It is subject to the definition of this specification.
Theory or mechanism described and disclosed herein, either right or wrong, should not in any way limit of the invention
Range, i.e. the content of present invention can be implemented in the case where not limited by any specific theoretical or mechanism.
Herein, all features defined in the form of numberical range or percentage range for example numerical value, quantity, content with it is dense
Degree is merely to succinctly and conveniently.Accordingly, the description of numberical range or percentage range should be regarded as having covered and specifically disclose institute
Individual number (including integer and score) in possible subranges and range.
It herein, for simplicity of description, can not to all of each technical characteristic in each embodiment or embodiment
The combination of energy is all described.Therefore, as long as there is no contradiction in the combination of these technical features, each embodiment or embodiment
In each technical characteristic can be combined arbitrarily, it is all possible combination be all considered to be this specification record model
It encloses.
Herein, term " containing ", " include " or " contain " indicate that various composition can be applied to mixing of the invention together
In object or composition.Therefore, term " mainly by ... form " and " by ... form " be included in term " containing ", " comprising " or
In "comprising".
The present inventor has found after extensive and in-depth study, is wrapped by using rubber to inorganic fire retardants
It covers, obtains the flame retardant microcapsule that inorganic fire retardants is capsule-core, rubber is capsule material, the surface of fire retardant and polymer can be enhanced
Bonding force, so that the compatibility and the dispersibility in resin of fire retardant and polymer significantly increase.Fire retardant of the invention is micro-
Capsule is used to prepare silicane crosslinking flame retardant polyolefin cable material with low smoke halogen, can increase the mobility of material in processing, improves
Processing performance can either reduce the probability of product precrosslink in process of production, while also accelerate the extruded velocity of product, mention
High efficiency；Thus obtained silicane crosslinking flame retardant polyolefin cable material with low smoke halogen has good mechanical strength, heat-resisting
Aging, resistance to heat distorsion and appearance are suitble to the production cables such as electric wire and transmission line class product.
Flame retardant microcapsule of the invention is the mixture of the inorganic fire retardants particle of rubber coated.Herein, " cladding "
One word has the conventional connotation of this field, can refer to the connotation of " cladding " in " coating modification " word.Those skilled in the art can
With understanding, in the present invention, cladding is not required for coating completely.
Being suitable for the invention rubber includes but is not limited to Liquid Ethylene Propylene Methylene and butyl rubber etc..In certain embodiments
In, being suitable for the invention rubber is Liquid Ethylene Propylene Methylene.In general, being suitable for the invention Liquid Ethylene Propylene Methylene and including but unlimited
In liquid ethylene-propylene-diene rubber, liquid dihydric EP rubbers or combinations thereof.In certain embodiments, it is suitable for the invention liquid
Body EP rubbers is selected from Trilene EP rubbers or EPM EP rubbers, and Trilene EP rubbers is raw for Uniroyal,Inc.
The resin of production, EPM EP rubbers are provided for De Shigu company, the U.S., are commercially available.
Being suitable for the invention inorganic fire retardants can be the inorganic fire retardants commonly used in the art in CABLE MATERIALS, including but not
It is limited to aluminium hydroxide and magnesium hydroxide etc..In certain embodiments, it is suitable for the invention the average grain diameter of inorganic fire retardants
In 800 mesh hereinafter, preferably 1000-5000 mesh.By buying or it can obtain average grain diameter using the conventional method of this field and exist
800 mesh aluminium hydroxide below or magnesium hydroxide.For example, in certain embodiments, present invention airslide disintegrating mill is by hydrogen-oxygen
Change aluminium and carry out ultra-fine grinding, its average grain diameter is made to be reduced to 800 mesh or less.Being suitable for the invention inorganic fire retardants can be hydrogen
The mixture of aluminium oxide and magnesium hydroxide；Without specifically limited, those skilled in the art can be used often two kinds of ratio in mixture
The method of rule determines optimal proportional region.
In general, the weight ratio of rubber and inorganic fire retardants in flame retardant microcapsule of the invention can be 10-50:100,
Such as 20-40:100 or 30-40:100 etc..
Flame retardant microcapsule of the invention can be prepared by the mixture of stirring inorganic fire retardants and rubber.It can be used
The conventional method of this field is stirred the mixture of inorganic fire retardants and rubber, so that rubber coated is in inorganic fire retardants
On.It is understood that the stirring is usually high-speed stirred；The method of high-speed stirred can be the conventional method of this field.?
In certain embodiments, the present invention carries out high-speed stirred in high-speed mixer, to inorganic fire retardants and rubber.Inorganic fire retardants
With rubber by stirring, after being uniformly dispersed, that is, flame retardant microcapsule is formed.
Silicane crosslinking flame retardant polyolefin cable material with low smoke halogen is usually by the A material containing fire retardant and the B containing catalyst
Expect that two kinds of formulas are prepared.A expects to usually contain polyolefin, fire retardant, antioxidant and the processing aid of Silane Grafted.B material is logical
Often contain polyolefin, catalyst, antioxidant and processing aid.
Therefore, the present invention also includes that the crosslinked with silicane containing flame retardant microcapsule described in any embodiment herein is low
The composition (A material) of cigarette phosphorus flame retardant etc..In general, composition (A material) of the invention is poly- containing Silane Grafted
Alkene, flame retardant microcapsule of the invention, antioxidant and processing aid.
The polyolefin for being suitable for the invention Silane Grafted can be the poly- of the Silane Grafted commonly used in the art in CABLE MATERIALS
Alkene, the including but not limited to low density polyethylene (LDPE) of Silane Grafted, the linear low density polyethylene of Silane Grafted, Silane Grafted
The ethylene-octene copolymerization of metallocene linear-low density polyethylene, the ethylene-vinyl acetate copolymer of Silane Grafted, Silane Grafted
Object etc..The polyolefin of Silane Grafted can be commercially available, and can also be adopted and be prepared with the conventional methods in the field, for example, can
With by polyolefin, silane crosslinker, initiator, antioxidant through mixing, extruding pelletization, be dried to obtain；Silane crosslinker can be selected from
Vinyltrimethoxysilane, vinyltriethoxysilane or combinations thereof；Initiator can be selected from cumyl peroxide, peroxide
Change di-tert-butyl or benzoyl peroxide；Antioxidant can be selected from antioxidant 1010, antioxidant 1135, antioxidant 300, antioxidant
168, anti-oxidant DLTP, antioxidant 1076 or combinations thereof.
Being suitable for the invention antioxidant (including the antioxidant in the antioxidant and B material in A material), to can be this field normal
For the antioxidant of CABLE MATERIALS, including but not limited to antioxidant 1010, antioxidant 1135, antioxidant 300, irgasfos 168, antioxygen
Agent DLTP, antioxidant 1076 or combinations thereof.The antioxidant in antioxidant and B material in composition (A material) of the invention can phase
Together, it can also be different.The dosage of antioxidant is had no it is specifically limited, can according to the dosage of this field routine use antioxidant.
Being suitable for the invention processing aid (including the processing aid in the processing aid and B material in A material) can be this
Field is usually used in the processing aid of CABLE MATERIALS, including but not limited to oleamide, polyethylene wax, polypropylene wax or combinations thereof.This
The processing aid in processing aid and B material in the composition (A material) of invention may be the same or different.To processing aid
Dosage have no it is specifically limited, can according to the dosage of this field routine use processing aid.
In general, composition (A material) of the invention may include the component of following parts by weight:
In certain embodiments, composition of the invention (A material) is particulate material form by squeezing out at 100-150 DEG C；
Preferably, described to be extruded as squeezing out using reciprocating single-bolt extruder.
The invention also includes the low cigarette of crosslinked with silicane containing flame retardant microcapsule described in any embodiment herein without
Halogen flame-proof polyolefine cable material, the silicane crosslinking flame retardant polyolefin cable material with low smoke halogen contain composition of the invention (A material)
Expect with B.
Being suitable for the invention polyolefin can be the polyolefin commonly used in the art in CABLE MATERIALS, including but not limited to low close
It is pungent to spend polyethylene, linear low density polyethylene, metallocene linear-low density polyethylene, ethylene-vinyl acetate copolymer, ethylene-
Alkene copolymer etc..The polyolefin in polyolefin and B material in the polyolefin of Silane Grafted in composition (A material) of the invention can
With identical, can also be different.
Being suitable for the invention catalyst can be the catalyst commonly used in the art in CABLE MATERIALS, and including but not limited to two is pungent
Base dibutyl tin, dibutyltin diacetate, dibutyl tin dilaurate etc..The dosage of catalyst is had no it is specifically limited, can root
Catalyst is used according to the dosage of this field routine.
In general, being suitable for the invention B material may include the component of following parts by weight:
In certain embodiments, B material is suitable for the invention by 140-190 DEG C of mixing.
In general, in silicane crosslinking flame retardant polyolefin cable material with low smoke halogen of the invention, composition of the invention (A material) with
The weight ratio of B material can be (90-99): (1-10), preferably (93-97): (3-7).
The invention also includes prepare the electricity of crosslinked with silicane low smoke halogen-free flame-retardant polyolefin described in any embodiment herein
The method of cable material.In general, this method comprises: according to required weight provide composition of the invention (A material) and B material
Each component；The each component of mixing A material simultaneously squeezes out at 100-150 DEG C, is granulated, and obtains A material particulate material；Mix each group of B material
Divide and be kneaded at 140-190 DEG C, is granulated, obtains B material particulate material；A is expected to squeeze after particulate material and B material particulate material mix
Out, the phosphorus flame retardant etc. of crosslinked with silicane is obtained.
The method that this field routine can be used squeezes out A material, is granulated.In certain embodiments, the present invention uses
Reciprocating single-bolt extruder squeezes out A material.
The method that this field routine can be used is kneaded B material, is granulated, such as kneading machine can be used to mix B material
Refining.
In general, A material particulate material and B material particulate material can be according to (90-99): (1-10), preferably (93-97): the weight of (3-7)
The mixing of amount ratio.After mixing, it can be squeezed out in 140-190 DEG C, obtain silane crosslinked halogen-free flame-retardant cable material of polyolefin.
Compared with prior art, the invention has the following beneficial effects:
After flame retardant microcapsule of the invention is mixed with the other components of cable material of polyolefin, increase the stream of material in processing
Dynamic property, improves processing performance, can either reduce the probability of product precrosslink in process of production, while also accelerating squeezing for product
Speed out improves production efficiency；The surface adhesion for enhancing polymer and inorganic fire retardants, also greatly with the compatibility of polymer
It improves, is conducive to dispersion of the fire retardant in resin, guarantees the slickness of product surface, improve the comprehensive performance of product.Tool
For body, tested by method described herein, the tensile strength of crosslinked with silicane fireproofing cable material without halide of the invention >=
11MPa, elongation at break >=160%, oxygen index (OI) >=29%, the tensile strength variation after air heat ageing (158 DEG C × 168h)
Rate≤18%, elongation at break change rate≤22%, heat extend≤75%, and material appearance reaches preferable rank or more, melt index
>=1.4g/10min has excellent mechanical performance, flame retardant property, heat aging property and good appearance.
Invention is further described in detail With reference to embodiment.It should be understood that these embodiments are only
Illustrative, the range being not intended to limit the present invention.For reagent, method, condition used in this paper and embodiment etc., unless
It is otherwise noted, is otherwise conventional reagent, method and condition.The test method of actual conditions is not specified in the following example,
Usually measure according to national standards.If without corresponding national standard, according to general international standard, normal condition or manufacture
Condition proposed by manufacturer carries out.Unless otherwise stated, otherwise all number is parts by weight, and all percentage is weight hundred
Divide ratio.
The raw material that embodiment 1-5 is used is as follows:
Liquid Ethylene Propylene Methylene: liquid ethylene-propylene-diene rubber；
The polyolefin of Silane Grafted: vinyltrimethoxysilane grafted linear low-density polyethylene；
A expects antioxidant: DLTP；
A expects processing aid: polyethylene wax；
Polyolefin: linear low density polyethylene；
Catalyst: dioctyl dibutyl tin；
B expects antioxidant: DLTP；
B expects processing aid: polyethylene wax.
Embodiment 1:
The flame retardant microcapsule of the present embodiment and the preparation process of crosslinked with silicane low-smoke non-halogen flame-retardant agent cable material of polyolefin
It is as follows:
One, the preparation of flame retardant microcapsule:
1. aluminium hydroxide is added in airslide disintegrating mill, carry out ultra-fine grinding, make its average grain diameter be reduced to 800 mesh with
Under, it is sealed；
2. aluminium hydroxide and 10 part by weight of liquid EP rubbers that in a high speed mixer, 100 parts by weight steps 1 are obtained
Carry out high-speed stirred.After being uniformly dispersed, flame retardant microcapsule is formed, is sealed.
Two, the preparation of the low smoke halogen-free fire retardant polyolefin cable material of crosslinked with silicane:
1, the preparation of A material
A is expected to carry out ingredient according to the component of following parts by weight:
The polyolefin, flame retardant microcapsule, A of the Silane Grafted of above-mentioned weight are expected that antioxidant and A material processing help
After agent mixing, feeding is kneaded at 100-150 DEG C, is sheared, is squeezed out, then through being subcooled in reciprocating single-bolt extruder
But, it is granulated, is dry, obtains A material.
2, the preparation of B material
B is expected to carry out ingredient according to the component of following parts by weight:
After polyolefin, catalyst, B the material antioxidant of above-mentioned weight, B material processing aid are mixed, mixing is used
Machine is kneaded at 140-190 DEG C, then through supercooling, granulation, drying, obtains B material.
3, the preparation of CABLE MATERIALS
Gained A material and gained B material are uniformly mixed by weight 95:5, squeezed out through extruder in 140-190 DEG C, as silicon
Alkane cross-linking low smoke halogen-free flame retardant CABLE MATERIALS.
Embodiment 2:
The flame retardant microcapsule of the present embodiment and the preparation process of crosslinked with silicane low-smoke non-halogen flame-retardant agent cable material of polyolefin
It is as follows:
One, the preparation of flame retardant microcapsule:
1. aluminium hydroxide is added in airslide disintegrating mill, carry out ultra-fine grinding, make its average grain diameter be reduced to 800 mesh with
Under, it is sealed；
2. aluminium hydroxide and 20 part by weight of liquid EP rubbers that in a high speed mixer, 100 parts by weight steps 1 are obtained
Carry out high-speed stirred.After being uniformly dispersed, flame retardant microcapsule is formed, is sealed.
Two, the preparation of the low smoke halogen-free fire retardant polyolefin cable material of crosslinked with silicane:
A is expected to carry out ingredient according to the component of following parts by weight:
B is expected to carry out ingredient according to the component of following parts by weight:
The preparation process of crosslinked with silicane fireproofing cable material without halide is the same as embodiment 1.
Embodiment 3:
The flame retardant microcapsule of the present embodiment and the preparation process of crosslinked with silicane low-smoke non-halogen flame-retardant agent cable material of polyolefin
It is as follows:
One, the preparation of flame retardant microcapsule:
1. aluminium hydroxide is added in airslide disintegrating mill, carry out ultra-fine grinding, make its average grain diameter be reduced to 800 mesh with
Under, it is sealed；
2. aluminium hydroxide and 30 part by weight of liquid EP rubbers that in a high speed mixer, 100 parts by weight steps 1 are obtained
Carry out high-speed stirred.After being uniformly dispersed, flame retardant microcapsule is formed, is sealed.
Two, the preparation of the low smoke halogen-free fire retardant polyolefin cable material of crosslinked with silicane:
A is expected to carry out ingredient according to the component of following parts by weight:
B is expected to carry out ingredient according to the component of following parts by weight:
The preparation process of crosslinked with silicane fireproofing cable material without halide is the same as embodiment 1.
Embodiment 4:
The flame retardant microcapsule of the present embodiment and the preparation process of crosslinked with silicane low-smoke non-halogen flame-retardant agent cable material of polyolefin
It is as follows:
One, the preparation of flame retardant microcapsule:
1. aluminium hydroxide is added in airslide disintegrating mill, carry out ultra-fine grinding, make its average grain diameter be reduced to 800 mesh with
Under, it is sealed；
2. aluminium hydroxide and 40 part by weight of liquid EP rubbers that in a high speed mixer, 100 parts by weight steps 1 are obtained
Carry out high-speed stirred.After being uniformly dispersed, flame retardant microcapsule is formed, is sealed.
Two, the preparation of the low smoke halogen-free fire retardant polyolefin cable material of crosslinked with silicane:
A is expected to carry out ingredient according to the component of following parts by weight:
B is expected to carry out ingredient according to the component of following parts by weight:
The preparation process of crosslinked with silicane fireproofing cable material without halide is the same as embodiment 1.
Embodiment 5:
The flame retardant microcapsule of the present embodiment and the preparation process of crosslinked with silicane low-smoke non-halogen flame-retardant agent cable material of polyolefin
It is as follows:
One, the preparation of flame retardant microcapsule:
1. aluminium hydroxide is added in airslide disintegrating mill, carry out ultra-fine grinding, make its average grain diameter be reduced to 800 mesh with
Under, it is sealed；
2. aluminium hydroxide and 50 part by weight of liquid EP rubbers that in a high speed mixer, 100 parts by weight steps 1 are obtained
Carry out high-speed stirred.After being uniformly dispersed, flame retardant microcapsule is formed, is sealed.
Two, the preparation of the low smoke halogen-free fire retardant polyolefin cable material of crosslinked with silicane:
A is expected to carry out ingredient according to the component of following parts by weight:
B is expected to carry out ingredient according to the component of following parts by weight:
The preparation process of crosslinked with silicane fireproofing cable material without halide is the same as embodiment 1.
The properties of the low smoke halogen-free fire retardant polyolefin cable material of the crosslinked with silicane of embodiment 1-5 are tested,
The results are shown in Table 1.In table 1, comparative example is (to surpass, trade mark DG-01) resistance in Luoyang using common modifications aluminium hydroxide on the market
Agent is fired, the crosslinked with silicane fireproofing cable material without halide referring to made from the formula and method of embodiment 1.
The test method and evaluation criterion of properties are as follows in table 1:
Tensile strength, elongation at break: according to 2951 standard test of GB/T；
Density: according to 1033.1 standard test of GB/T；
Oxygen index (OI): according to 2406 standard test of GB/T；
Air heat ageing: CABLE MATERIALS is cut out into sample according to GB/T 2951, batten is as aging is carried out in air aging case, always
Changing temperature is 180 DEG C, ageing time 168h, then according to 2951 test bars tensile strength of GB/T and elongation at break；
Heat extends: according to 2951.21 standard test of GB/T；
Material appearance: if material surface is smooth, color is uniform, and it is good to be considered as appearance；If material surface particle is less,
It is preferable to be considered as appearance there are uneven color phenomenon for small part；If material surface is rougher, particle is more, and color is more uneven
It is even, it is general to be considered as appearance；
Melt index: referring to GB/T 3682-2000 standard test.
Table 1: the performance test results of embodiment 1-5 and comparative example crosslinked with silicane fireproofing cable material without halide
The present invention makees capsule material coated inorganic fire retardant (such as aluminium hydroxide) using rubber (such as Liquid Ethylene Propylene Methylene), using object
The flame retardant microcapsule for managing cladding process (if first airslide disintegrating mill crushes, rear high-speed mixer mixing) preparation is used to prepare crosslinkable silane
Join fireproofing cable material without halide.As can be seen from Table 1, the drawing of the crosslinked with silicane fireproofing cable material without halide of embodiment 1-5
Intensity is stretched higher than comparative example, shows it with higher mechanical strength.Embodiment 2-5 crosslinked with silicane fireproofing cable material without halide
Elongation at break be higher than comparative example, show it with higher toughness.The crosslinked with silicane low-smoke non-halogen flame-retardant electricity of embodiment 1-5
Tensile strength change rate and elongation at break change rate of the cable material after undergoing air heat ageing (158 DEG C × 168h) are lower than comparison
Example, shows it with better heat-resistant aging.The heat of the crosslinked with silicane fireproofing cable material without halide of embodiment 1-5 extends low
In comparative example, show it with better resistance to heat distorsion.The crosslinked with silicane fireproofing cable material without halide of embodiment 2-4 is compared
Comparative example has more preferably appearance.It can be seen that the crosslinked with silicane low-smoke non-halogen flame-retardant of the invention containing flame retardant microcapsule
CABLE MATERIALS has better comprehensive performance.
Embodiment 6:
The flame retardant microcapsule of the present embodiment and the preparation process of crosslinked with silicane low-smoke non-halogen flame-retardant agent cable material of polyolefin
It is as follows:
One, the preparation of flame retardant microcapsule:
1. aluminium hydroxide is added in airslide disintegrating mill, carry out ultra-fine grinding, make its average grain diameter be reduced to 800 mesh with
Under, it is sealed；
2. aluminium hydroxide and 30 part by weight of liquid EP rubbers that in a high speed mixer, 100 parts by weight steps 1 are obtained
Carry out high-speed stirred.After being uniformly dispersed, flame retardant microcapsule is formed, is sealed.
Two, the preparation of the low smoke halogen-free fire retardant polyolefin cable material of crosslinked with silicane:
A is expected to carry out ingredient according to the component of following parts by weight:
B is expected to carry out ingredient according to the component of following parts by weight:
The preparation process of crosslinked with silicane fireproofing cable material without halide is the same as embodiment 1.
The crosslinked with silicane fireproofing cable material without halide that this embodiment is prepared is tested according to the above method, is stretched strong
Degree >=11MPa, elongation at break >=180%, oxygen index (OI) >=29%, the tensile strength after air heat ageing (158 DEG C × 168h)
Change rate≤18%, elongation at break change rate≤20%, heat extend≤75%, melt index >=1.4g/10min, outside material
It sees preferable.
Embodiment 7:
The flame retardant microcapsule of the present embodiment and the preparation process of crosslinked with silicane low-smoke non-halogen flame-retardant agent cable material of polyolefin
It is as follows:
One, the preparation of flame retardant microcapsule:
1. aluminium hydroxide is added in airslide disintegrating mill, ultra-fine grinding is carried out, its average grain diameter is made to be reduced to 1000 mesh
Hereinafter, being sealed；
2. the aluminium hydroxide that in a high speed mixer, 100 parts by weight steps 1 are obtained and 30 parts by weight butyl rubbers carry out
High-speed stirred.After being uniformly dispersed, flame retardant microcapsule is formed, is sealed.
Two, the preparation of the low smoke halogen-free fire retardant polyolefin cable material of crosslinked with silicane:
A is expected to carry out ingredient according to the component of following parts by weight:
B is expected to carry out ingredient according to the component of following parts by weight:
The preparation process of crosslinked with silicane fireproofing cable material without halide is the same as embodiment 1.
The crosslinked with silicane fireproofing cable material without halide that this embodiment is prepared is tested according to the above method, is stretched strong
Degree >=11MPa, elongation at break >=180%, oxygen index (OI) >=29%, the tensile strength after air heat ageing (158 DEG C × 168h)
Change rate≤18%, elongation at break change rate≤20%, heat extend≤75%, melt index >=1.4g/10min, outside material
It sees preferable.
The above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to preferred embodiment to this hair
It is bright to be described in detail, those skilled in the art should understand that, it can modify to technical solution of the present invention
Or equivalent replacement should all cover without departing from the objective and range of technical solution of the present invention in claim of the invention
In range.
All references mentioned in the present invention is incorporated herein by reference, independent just as each document
It is incorporated as with reference to such.In addition, it should also be understood that, those skilled in the art can be right after having read above content of the invention
The present invention makes various changes or modifications, and such equivalent forms equally fall within the appended claims limited range of the present invention.
Claims (10)
1. a kind of flame retardant microcapsule, which is characterized in that the flame retardant microcapsule is the inorganic fire retardants of rubber coated.
2. flame retardant microcapsule as described in claim 1, which is characterized in that the weight ratio of the rubber and inorganic fire retardants is
10-50:100, preferably 20-40:100, more preferably 30-40:100.
3. flame retardant microcapsule as described in claim 1, which is characterized in that the rubber is Liquid Ethylene Propylene Methylene, butyl rubber
Glue or combinations thereof；Preferably, the Liquid Ethylene Propylene Methylene is selected from liquid ethylene-propylene-diene rubber, liquid dihydric EP rubbers or its group
It closes；And/or
The inorganic fire retardants is selected from aluminium hydroxide, magnesium hydroxide or combinations thereof；Preferably, the average grain of the inorganic fire retardants
Diameter≤800 mesh, preferably in the range of 1000-5000 mesh.
4. a kind of method for preparing flame retardant microcapsule as claimed in any one of claims 1-3, which is characterized in that the side
Method includes stirring the mixture of inorganic fire retardants and rubber, thus to obtain the flame retardant microcapsule.
5. the flame retardant microcapsule being prepared using method as claimed in claim 4.
6. a kind of crosslinked with silicane low smoke and zero halogen resistance containing the flame retardant microcapsule as described in any one of claim 1-3 or 5
Fire the composition of cable material of polyolefin, which is characterized in that the composition contains the following parts by weight:
Optionally, the composition is to squeeze out by 100-150 DEG C；Preferably, described to be extruded as squeezing using reciprocating single screw rod
Machine squeezes out out.
7. a kind of crosslinked with silicane low smoke and zero halogen resistance containing the flame retardant microcapsule as described in any one of claim 1-3 or 5
Firing cable material of polyolefin, which is characterized in that the cable material of polyolefin includes that A material and B expect,
The A material contains the following parts by weight:
The B material contains the following parts by weight:
Preferably, in the cable material of polyolefin, the weight ratio of A material and B material is (90-99): (1-10).
8. silicane crosslinking flame retardant polyolefin cable material with low smoke halogen as claimed in claim 7, which is characterized in that in the A material,
The dosage of the flame retardant microcapsule be 50-80 parts by weight, and in flame retardant microcapsule rubber and inorganic fire retardants weight ratio
It is (93-97): (3-7) for 30-40:100 and A material and the weight ratio of B material.
9. a kind of method for preparing silicane crosslinking flame retardant polyolefin cable material with low smoke halogen as claimed in claim 7 or 8, special
Sign is that described method includes following steps:
Each component of A material and B material is provided；
It mixes A and expects each component, and squeezed out in 100-150 DEG C, is granulated, obtain A material particulate material；Preferably, it is described be extruded as using
Reciprocating single-bolt extruder squeezes out；
It mixes B and expects each component, and be kneaded in 140-190 DEG C, is granulated, obtain B material particulate material；With
The A material particulate material and B material particulate material are mixed, is squeezed out at 140-190 DEG C；
Thus the phosphorus flame retardant etc. of crosslinked with silicane is obtained；
Preferably, the A material particulate material and B material particulate material are according to (90-99): the weight ratio mixing of (1-10).
10. the silicane crosslinking flame retardant polyolefin cable material with low smoke halogen being prepared using method as claimed in claim 9.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101037600A (en) * | 2006-03-17 | 2007-09-19 | 上海杰事杰新材料股份有限公司 | Microencapsulation inorganic flaming-resistant agent and preparation method thereof |
| CN101633754A (en) * | 2009-05-22 | 2010-01-27 | 上海凯波特种电缆料厂有限公司 | Oil resistant type silane natural cross-linking low smoke halogen-free flame retardant polyolefin cable material and preparation method thereof |
| CN107304299A (en) * | 2016-04-21 | 2017-10-31 | 中国石油化工股份有限公司 | A kind of fire retardant, flame-retardant pitch and preparation method thereof |
| CN107857945A (en) * | 2017-11-10 | 2018-03-30 | 安徽龙川橡塑科技有限公司 | A kind of environmental protection flame retardant ethylene propylene diene rubber vibration-absorptive material and preparation method thereof |
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2018
- 2018-12-29 CN CN201811638736.6A patent/CN109679143A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101037600A (en) * | 2006-03-17 | 2007-09-19 | 上海杰事杰新材料股份有限公司 | Microencapsulation inorganic flaming-resistant agent and preparation method thereof |
| CN101633754A (en) * | 2009-05-22 | 2010-01-27 | 上海凯波特种电缆料厂有限公司 | Oil resistant type silane natural cross-linking low smoke halogen-free flame retardant polyolefin cable material and preparation method thereof |
| CN107304299A (en) * | 2016-04-21 | 2017-10-31 | 中国石油化工股份有限公司 | A kind of fire retardant, flame-retardant pitch and preparation method thereof |
| CN107857945A (en) * | 2017-11-10 | 2018-03-30 | 安徽龙川橡塑科技有限公司 | A kind of environmental protection flame retardant ethylene propylene diene rubber vibration-absorptive material and preparation method thereof |
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Effective date of registration: 20210603 Address after: 268 beihengshahe Road, Minhang District, Shanghai 201108 Applicant after: Shanghai Zhizheng New Material Co., Ltd Address before: 268 beihengshahe Road, Xinzhuang Industrial Zone, Minhang District, Shanghai 201108 Applicant before: SHANGHAI ORIGINALDOW ADVANCED COMPOUNDS Co.,Ltd. |
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Application publication date: 20190426 |