CN106221220A - A kind of organosilicon multi-fuactional master-batch of fire-resistant cable material and preparation method thereof - Google Patents
A kind of organosilicon multi-fuactional master-batch of fire-resistant cable material and preparation method thereof Download PDFInfo
- Publication number
- CN106221220A CN106221220A CN201610596104.2A CN201610596104A CN106221220A CN 106221220 A CN106221220 A CN 106221220A CN 201610596104 A CN201610596104 A CN 201610596104A CN 106221220 A CN106221220 A CN 106221220A
- Authority
- CN
- China
- Prior art keywords
- parts
- silicone rubber
- master
- batch
- fuactional
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/46—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes silicones
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/29—Protection against damage caused by extremes of temperature or by flame
- H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
Abstract
A kind of organosilicon multi-fuactional master-batch of fire-resistant cable material and preparation method thereof, according to mass fraction meter, including the silicone rubber of 90～120 parts, the ethylene vinyl acetate polymer of 35～60 parts, the Polyolefin Grafted Maleic Anhydride of 35～55 parts, the organic fatty hydrochlorate of 40～120 parts, the white carbon of 80～110 parts and the metal-oxide of 10～65 parts.By super mixer by metal-oxide, white carbon mix homogeneously, obtain compound A；Again silicone rubber, ethylene vinyl acetate polymer, Polyolefin Grafted Maleic Anhydride, organic fatty hydrochlorate and compound A are put into successively and banbury carries out banburying.The present invention can be significantly increased the oxygen index (OI) of material, improves drip phenomenon during material combustion, and fire-resistant synergistic effect is notable；The flexibility under the mechanical property of material, anti-cracking performance and low temperature can be improved；Can improve drawing abillity, preparation method is easy, low cost.
Description
Technical field
The present invention relates to fire-resistant cable material and technical field of modification thereof, be specifically related to the organosilicon of a kind of fire-resistant cable material
Multi-fuactional master-batch and preparation method thereof.
Background technology
In recent years, low-smoke halogen-free flame-proof cable material because of its environmental protection, press down the advantages such as cigarette is nontoxic and enjoy favor, and by
Gradually become the main flow of development.In order to reach certain flame-retardancy requirements, general halogen-free flame retardants (such as metal hydroxides etc.) adds
Dosage is the biggest, and bigger loading will certainly affect mechanical characteristic and the processing characteristics of material.Therefore, halogen-free flameproof electricity
Cable material in actual applications, is often faced with between mechanical property, processing characteristics and fire resistance mutually restriction and can not take into account
Problem.
The processing characteristics of bittern-free flame-proof material typically can be improved by adding lubricant, and effect is preferable.Compare it
Under, although the means improving mechanical property have a lot, as used bulking agent, fire-retardant filler ultra fine and surface coupling processing
Deng, but some inherent shortcomings under high occupied state cannot be overcome all the time.Such as, even if filler processes through surface, at base
Still can there is skewness in body material, assemble pockets of phenomenon, this can cause the interface between fire-retardant filler and matrix resin to tie
Make a concerted effort to weaken, ultimately result in the mechanical properties decrease of material.Meanwhile, polymeric matrix differs with the thermal coefficient of expansion of fire-retardant filler
The biggest, easily occur at the interface of the two separating during expanding with heat and contract with cold, so the Halogen resistance under high occupied state
Combustible material is prone to cracking.In order to fundamentally overcome the fire-retardant filler all drawbacks when height is filled, many scholars throw oneself into
The amount of filling out multi-functional, low, high efficiency modifying agent research and development in the middle of.
Organic silicon fibre retardant be development in recent years get up a kind of high-efficiency low-toxicity, the novel halogen-free flame-retardant agent of environmental protection,
It is typically used as retardant synergist, compounds in thermoplastic resin with metal hydroxides or expansion type flame retardant.Merit attention
, organic silicon fibre retardant the most also has the function of processing aid concurrently, and it is reducing main flame retardant consumption, is improving flame retarding efficiency
Meanwhile, generally can also increase main flame retardant dispersibility in the base, thus improve the mechanical property of material to a certain extent
And processing characteristics.The commercial prod of organic silicon fibre retardant is few, and silicones and silicone powder are that modal fire-resistant synergistic has
Machine silicon product, but both with polyolefin etc. the compatibility of material the best, fire-retardant and modified effect does not includes the most outstanding yet, and price
Of a relatively high, therefore use the most extensive.Chinese patent application 200610123965.5 discloses a kind of by chemosynthesis legal system
Standby Silicious fire retard ant for polyolefin, its addition is little, less to mechanics influence, and flame retardant effect is excellent, but Preparation equipment and work
Skill is the most complex, and manufacturing cost is of a relatively high.
It addition, widely used silicone master batch and silicone powder are also with organosilicon as primary raw material in CABLE MATERIALS field
And the product prepared.Although both fire-resistant synergistic limited use and expensive, but it is in the case of addition is less
There is more significantly lubrication, therefore be usually used in improving drawing abillity and improving the surface property of material.But, this kind of
The function of product is the most single, does not gives full play to the fire-resistant synergistic of wherein silicone ingredients, improves the effect of mechanical property.
Summary of the invention
It is an object of the invention to overcome the shortcoming of prior art, it is provided that a kind of advantage of lower cost and combination property are more
Excellent organosilicon multi-fuactional master-batch of fire-resistant cable material and preparation method thereof.
For achieving the above object, the present invention adopts the following technical scheme that:
The organosilicon multi-fuactional master-batch of a kind of fire-resistant cable material, according to mass fraction meter, including 90～120 parts
Silicone rubber, the ethene-vinyl acetate polymer of 35～60 parts, the Polyolefin Grafted Maleic Anhydride of 35～55 parts, 40～120 parts
Organic fatty hydrochlorate, the white carbon of 80～110 parts and the metal-oxide of 10～65 parts.
The present invention is further improved by, and described silicone rubber is the poly-silicon of the high molecular with reactive functional
Oxygen alkane.
The present invention is further improved by, and in described ethene-vinyl acetate polymer, vinyl acetate mass content is
12%～40%, melt index is 2～20g/10min；Silicone rubber is methyl phenyl silicone rubber, methyl vinyl silicone rubber, first
Base phenyl vinyl silicone rubber, phenylene silicone rubber or phenylate 1,2-ethylidene silicone rubber.
The present invention is further improved by, and described Polyolefin Grafted Maleic Anhydride is maleic anhydride grafted polyethylene, horse
One or more in maleic anhydride grafted POE, maleic anhydride inoculated polypropylene, maleic anhydride grafting EVA.
The present invention is further improved by, and described organic fatty hydrochlorate is in zinc stearate, barium stearate, calcium stearate
One or more.
The present invention is further improved by, and the particle diameter of described white carbon is less than 3 microns.
The present invention is further improved by, described metal-oxide be zinc oxide, magnesium oxide, nickel oxide, titanium dioxide,
One or more in aluminium sesquioxide.
The preparation method of the organosilicon multi-fuactional master-batch of a kind of fire-resistant cable material, comprises the following steps:
1) weighing: according to mass fraction meter, weigh the silicone rubber of 90～120 parts, the ethene-vinyl acetate of 35～60 parts gathers
Compound, the Polyolefin Grafted Maleic Anhydride of 35～55 parts, the organic fatty hydrochlorate of 40～120 parts, the white carbon of 80～110 parts with
And the metal-oxide of 10～65 parts；
2) material mixing: by super mixer by load weighted metal-oxide, white carbon mix homogeneously, mixed
Material A；
3) banburying: load weighted silicone rubber, ethene-vinyl acetate polymer are thrown together with Polyolefin Grafted Maleic Anhydride
Enter in banbury, banburying 3～5 minutes within the temperature range of 90 DEG C～110 DEG C；Load weighted organic fatty hydrochlorate is added
In banbury, banburying 5～10 minutes within the temperature range of 100～120 DEG C；Compound A is divided into two parts by weight, depends on
Secondary joining in banbury, all banburying 5～15 minutes within the temperature range of 110～160 DEG C after adding, final preparing is hindered every time
The organosilicon multi-fuactional master-batch of combustion CABLE MATERIALS.
The present invention is further improved by, and described silicone rubber is the poly-silicon of the high molecular with reactive functional
Oxygen alkane,
In described ethene-vinyl acetate polymer, vinyl acetate mass content is 12%～40%, melt index be 2～
20g/10min；
Described Polyolefin Grafted Maleic Anhydride is maleic anhydride grafted polyethylene, maleic anhydride is grafted POE, maleic anhydride connects
One or more in branch polypropylene, maleic anhydride grafting EVA；
Described organic fatty hydrochlorate is one or more in zinc stearate, barium stearate, calcium stearate；
The particle diameter of described white carbon is less than 3 microns；
Described metal-oxide is the one in zinc oxide, magnesium oxide, nickel oxide, titanium dioxide, aluminium sesquioxide or many
Kind.
The present invention is further improved by, and is added by prepared multi-fuactional master-batch and pulverizes to pulverizer,
Obtain multi-fuactional master-batch powder；Silicone rubber is methyl phenyl silicone rubber, methyl vinyl silicone rubber, methyl phenyl vinyl
Silicone rubber, phenylene silicone rubber or phenylate 1,2-ethylidene silicone rubber.
Compared with prior art and product, there is advantages that
1. fire-resistant synergistic effect is notable.Organic fatty hydrochlorate, metal-oxide, white carbon are carried out by the present invention with silicone rubber
Compounding, can be catalyzed and participate in the formation of carborundum coking sealing coat when material combustion, thus strengthen condensed phase flame retardant effect.Cause
This, the present invention has the highest flame retarding efficiency, just can increase substantially oxygen index (OI) and avoid drippage in the case of consumption is less
The generation of phenomenon.Meanwhile, the present invention also helps and improves vertical combustion characteristic and reduce the consumption of inorganic combustion inhibitor, not Halogen
Element, environmental protection, there is preferable application prospect.
2. can improve the mechanical property of material.Silicone rubber is poor with the compatibility of high polymer, therefore the interpolation of silicon rubber
The use of agent would generally affect the mechanical property of material.Silicone rubber i.e. the gathering with reactive functional that the present invention is introduced
Siloxanes can form the connection of chemical bond during melt blending by situ-formed graft etc. between reaction and matrix resin, thus pole
The earth improves the compatibility of silicone rubber and matrix resin, and improves the mechanical property of composite.Additionally, the present invention and inorganic resistance
Combustion agent can mutually improve dispersity the most in the polymer when sharing, and this is also advantageous for changing of composite materials property
Kind.
3. can improve the flexibility under the anti-cracking performance of material and low temperature.Silicone rubber in the present invention and matrix resin
Between interface bond strength big, this can significantly increase the pliability of material, even if making material when high inorganic fill
Also there is the flexibility under excellent cracking resistance ability and low temperature.
4. have the effect of processing aid concurrently, there is price advantage.Compared with the product such as silicone master batch, silicone powder, this
Publicly price-reduction low materials processing torque, the effect improving materials processing performance are the most notable.Meanwhile, expensive in the present invention
The content of silicone rubber is relatively low, therefore has the advantage of low cost compared with silicone master batch, silicone powder.
Preparation method the most of the present invention is easy, low cost, beneficially industrialization large-scale production.
Further, in the present invention, the particle diameter of white carbon is less than 3 microns, why uses micron order not use nanometer
Level, is in order under conditions of ensureing to have enough dispersibility, it is to avoid the reunion between granule.
Detailed description of the invention
In order to make the object, technical solutions and advantages of the present invention clearer, carry out further below in conjunction with example
Describing in detail, example described herein is only used for explaining the present invention, is not intended to limit the present invention.
Embodiment 1
A kind of organosilicon multi-fuactional master-batch of fire-resistant cable material, according to quality meter, including: silicone rubber: 1200g；
Ethene-vinyl acetate polymer (EVA): 400g；Polyolefin Grafted Maleic Anhydride: 500g；Organic fatty hydrochlorate: 500g；Linesless charcoal
Black: 1000g；Metal-oxide: 500g.
Described silicone rubber is methyl vinyl silicone rubber；
In described ethene-vinyl acetate polymer (EVA), vinyl acetate mass content is 40%, and melt index is 3g/
10min；
Described Polyolefin Grafted Maleic Anhydride is that maleic anhydride is grafted POE；
Described organic fatty hydrochlorate is barium stearate；
The particle diameter of described white carbon is less than 3 microns；
Described metal-oxide is zinc oxide.
The preparation method of the above-mentioned multi-fuactional master-batch for fire-retardant electrical materials and appliances, comprises the following steps:
1) weighing: silicone rubber: 1200g；Ethene-vinyl acetate polymer (EVA): 400g；Polyolefin Grafted Maleic Anhydride:
500g；Organic fatty hydrochlorate: 500g；White carbon: 1000g；Metal-oxide: 500g；
2) material mixing: by super mixer by load weighted metal-oxide, white carbon mix homogeneously, mixed
Material A；
3) banburying: by load weighted silicone rubber, ethene-vinyl acetate polymer (EVA) and Polyolefin Grafted Maleic Anhydride
Put into together in banbury, banburying 5 minutes at a temperature of 90 DEG C；Load weighted organic fatty hydrochlorate is joined banbury
In, banburying 8 minutes at a temperature of 110 DEG C；Compound A is divided into two parts by weight, is added sequentially in banbury, every time
Equal banburying 10 minutes at a temperature of 160 DEG C after addition, finally prepare multi-fuactional master-batch；
4) pulverize: prepared multi-fuactional master-batch is added and pulverizes to pulverizer, obtain multifunctional modification female
Material powder.
Embodiment 2
A kind of organosilicon multi-fuactional master-batch of fire-resistant cable material, according to quality meter, including: silicone rubber: 1000g；
Ethene-vinyl acetate polymer (EVA): 600g；Polyolefin Grafted Maleic Anhydride: 450g；Organic fatty hydrochlorate: 1100g；Linesless charcoal
Black: 1100g；Metal-oxide: 100g.
Described silicone rubber is methyl phenyl vinyl silicone rubber；
In described ethene-vinyl acetate polymer (EVA), vinyl acetate mass content is 28%, and melt index is 3g/
10min；
Described Polyolefin Grafted Maleic Anhydride is that maleic anhydride is grafted EVA；
Described organic fatty hydrochlorate is zinc stearate；
The particle diameter of described white carbon is less than 3 microns；
Described metal-oxide is nickel oxide.
The preparation method of the above-mentioned multi-fuactional master-batch for fire-retardant electrical materials and appliances, comprises the following steps:
1) weighing: silicone rubber: 1000g；Ethene-vinyl acetate polymer (EVA): 600g；Polyolefin Grafted Maleic Anhydride:
450g；Organic fatty hydrochlorate: 1100g；White carbon: 1100g；Metal-oxide: 100g；
2) material mixing: by super mixer by load weighted metal-oxide, white carbon mix homogeneously, mixed
Material A；
3) banburying: by load weighted silicone rubber, ethene-vinyl acetate polymer (EVA) and Polyolefin Grafted Maleic Anhydride
Put into together in banbury, banburying 3 minutes at a temperature of 100 DEG C；Load weighted organic fatty hydrochlorate is joined banburying
In machine, banburying 7 minutes at a temperature of 100 DEG C；Compound A is divided into two parts by weight, is added sequentially in banbury, often
Equal banburying 15 minutes at a temperature of 150 DEG C after secondary addition, finally prepare multi-fuactional master-batch；
4) pulverize: prepared multi-fuactional master-batch is added and pulverizes to pulverizer, obtain multifunctional modification female
Material powder.
Embodiment 3
A kind of organosilicon multi-fuactional master-batch of fire-resistant cable material, according to mass fraction meter, including: silicone rubber: 900
Part；Ethene-vinyl acetate polymer (EVA): 350 parts；Polyolefin Grafted Maleic Anhydride: 350 parts；Organic fatty hydrochlorate: 400
Part；White carbon: 800 parts；Metal-oxide: 650 parts.
Described silicone rubber is methyl phenyl silicone rubber；
In described ethene-vinyl acetate polymer (EVA), vinyl acetate mass content is 12%, and melt index is 2g/
10min；
Described Polyolefin Grafted Maleic Anhydride is maleic anhydride grafted polyethylene；
Described organic fatty hydrochlorate is calcium stearate；
The particle diameter of described white carbon is less than 3 microns；
Described metal-oxide is magnesium oxide.
The preparation method of the above-mentioned multi-fuactional master-batch for fire-retardant electrical materials and appliances, comprises the following steps:
1) weighing: according to mass fraction meter, including: silicone rubber: 900 parts；Ethene-vinyl acetate polymer (EVA): 350
Part；Polyolefin Grafted Maleic Anhydride: 350 parts；Organic fatty hydrochlorate: 400 parts；White carbon: 800 parts；Metal-oxide: 650 parts；
2) material mixing: by super mixer by load weighted metal-oxide, white carbon mix homogeneously, mixed
Material A；
3) banburying: by load weighted silicone rubber, ethene-vinyl acetate polymer (EVA) and Polyolefin Grafted Maleic Anhydride
Put into together in banbury, banburying 4 minutes at a temperature of 110 DEG C；Load weighted organic fatty hydrochlorate is joined banburying
In machine, banburying 10 minutes at a temperature of 105 DEG C；Compound A is divided into two parts by weight, is added sequentially in banbury,
Equal banburying 5 minutes at a temperature of 110 DEG C add every time after, finally prepare multi-fuactional master-batch；
4) pulverize: prepared multi-fuactional master-batch is added and pulverizes to pulverizer, obtain multifunctional modification female
Material powder.
Embodiment 4
A kind of organosilicon multi-fuactional master-batch of fire-resistant cable material, according to mass fraction meter, including: silicone rubber:
1100 parts；Ethene-vinyl acetate polymer (EVA): 500 parts；Polyolefin Grafted Maleic Anhydride: 550 parts；Organic fatty hydrochlorate:
1200 parts；White carbon: 900 parts；Metal-oxide: 300 parts.
Described silicone rubber is phenylene silicone rubber；
In described ethene-vinyl acetate polymer (EVA), vinyl acetate mass content is 26%, and melt index is 20g/
10min；
Described Polyolefin Grafted Maleic Anhydride is maleic anhydride inoculated polypropylene；
Described organic fatty hydrochlorate is the mixture of zinc stearate and barium stearate；
The particle diameter of described white carbon is less than 3 microns；
Described metal-oxide is the mixture of titanium dioxide and aluminium sesquioxide.
The preparation method of the above-mentioned multi-fuactional master-batch for fire-retardant electrical materials and appliances, comprises the following steps:
1) weighing: according to mass fraction meter, including: silicone rubber: 900 parts；Ethene-vinyl acetate polymer (EVA): 350
Part；Polyolefin Grafted Maleic Anhydride: 350 parts；Organic fatty hydrochlorate: 400 parts；White carbon: 800 parts；Metal-oxide: 650 parts.
2) material mixing: by super mixer by load weighted metal-oxide, white carbon mix homogeneously, mixed
Material A；
3) banburying: by load weighted silicone rubber, ethene-vinyl acetate polymer (EVA) and Polyolefin Grafted Maleic Anhydride
Put into together in banbury, banburying 4 minutes at a temperature of 95 DEG C；Load weighted organic fatty hydrochlorate is joined banbury
In, banburying 5 minutes at a temperature of 120 DEG C；Compound A is divided into two parts by weight, is added sequentially in banbury, every time
Equal banburying 12 minutes at a temperature of 120 DEG C after addition, finally prepare multi-fuactional master-batch；
4) pulverize: prepared multi-fuactional master-batch is added and pulverizes to pulverizer, obtain multifunctional modification female
Material powder.
Embodiment 5
A kind of organosilicon multi-fuactional master-batch of fire-resistant cable material, according to mass fraction meter, including: silicone rubber:
1100 parts；Ethene-vinyl acetate polymer (EVA): 500 parts；Polyolefin Grafted Maleic Anhydride: 550 parts；Organic fatty hydrochlorate:
1200 parts；White carbon: 900 parts；Metal-oxide: 300 parts.
Described silicone rubber is phenylate 1,2-ethylidene silicone rubber；
In described ethene-vinyl acetate polymer (EVA), vinyl acetate mass content is 19%, and melt index is 10g/
10min；
Described Polyolefin Grafted Maleic Anhydride is that maleic anhydride is grafted POE；
Described organic fatty hydrochlorate is the mixture of zinc stearate, barium stearate and calcium stearate；
The particle diameter of described white carbon is less than 3 microns；
Described metal-oxide is the mixture of magnesium oxide, nickel oxide and titanium dioxide.
The preparation method of the above-mentioned multi-fuactional master-batch for fire-retardant electrical materials and appliances, comprises the following steps:
1) weighing: according to mass fraction meter, including: silicone rubber: 900 parts；Ethene-vinyl acetate polymer (EVA): 350
Part；Polyolefin Grafted Maleic Anhydride: 350 parts；Organic fatty hydrochlorate: 400 parts；White carbon: 800 parts；Metal-oxide: 650 parts.
2) material mixing: by super mixer by load weighted metal-oxide, white carbon mix homogeneously, mixed
Material A；
3) banburying: by load weighted silicone rubber, ethene-vinyl acetate polymer (EVA) and Polyolefin Grafted Maleic Anhydride
Put into together in banbury, banburying 5 minutes at a temperature of 100 DEG C；Load weighted organic fatty hydrochlorate is joined banburying
In machine, banburying 8 minutes at a temperature of 110 DEG C；Compound A is divided into two parts by weight, is added sequentially in banbury, often
Equal banburying 10 minutes at a temperature of 130 DEG C after secondary addition, finally prepare multi-fuactional master-batch；
4) pulverize: prepared multi-fuactional master-batch is added and pulverizes to pulverizer, obtain multifunctional modification female
Material powder.
Application Example 1
By investigating the modified effect of the multi-fuactional master-batch (hereinafter referred to as ZD) that the present invention is obtained, by embodiment 1 institute
Obtain product to add in ethene-vinyl acetate polymer/LLDPE Blends (EVA/LLDPE), and by it
Properties and ethene-vinyl acetate polymer/linear low density polyethylene/aluminium hydroxide/magnesium hydroxide co-mixing system (EVA/
LLDPE/ATH/MH) contrast.Sample preparation uses double roller mill, stamping technique.Mechanics Performance Testing, by GB/T
1040.2 2006 are carried out；Oxygen index (OI) is tested, and carries out by GB/T 2406.2 2009.Test result is shown in Table 1.
Table 1
| Formula number | Oxygen index (OI) | Whether drip | Hot strength/MPa | Elongation at break/% |
| 1#, EVA/LLDPE | 18.5 | It is | 14.2 | 847.1 |
| 2#, EVA/LLDPE/ATH/MH | 21 | It it is (on a small quantity) | 11.1 | 312.5 |
| 3#, EVA/LLDPE/ZD | 22 | No | 11.6 | 457.1 |
Note: ATH/MH, 65phr in table；ZD, 26phr.
As shown in Table 1, the fire retardation of 26 parts of ZD and 65 parts of metal hydroxidess is suitable, and the former is to material mechanical performance
Impact be significantly less than the latter.Additionally, when testing oxygen index (OI), the 2# formula that with the addition of 65 parts of hydroxide still has a small amount of dripping
Falling, the 3# formula that only with the addition of 26 parts of ZD then generates covering shell at material combustion, and drip phenomenon disappears.This shows in burning
During, the organosilicon in ZD can react and be formed structure charcoal with carbochain, therefore has and significantly hinders drip effect.
Application Example 2
Obtained for embodiment 2 product is added to ethene-vinyl acetate polymer/Low Density Polyethylene/maleic anhydride grafting
In EVA/ magnesium hydroxide co-mixing system (EVA/LDPE/EVA-g-MAH/MH) system, and their performance is contrasted.Meter
The consumption of EVA/LDPE is 100 parts, and in the most each formula, EVA-g-MAH consumption is that the consumption of 20phr, ZD and MH is listed in table 2.Sample
Preparation and method of testing are identical with Application Example 1, and test result is shown in Table 2.
Table 2
As shown in Table 2, the addition of ZD can be significantly increased the oxygen index (OI) of EVA/LDPE/EVA-g-MAH/MH system.Only
The ZD adding 5phr just can make the oxygen index (OI) of material improve to 32 (7# formula) from 27 (6# formula), and along with the increasing of ZD addition
Adding, the oxygen index (OI) of system presents the trend being gradually increased.Understand in conjunction with the oxygen index (OI) of 4#, 5#, 6# and 11# in table, low at MH
In the case of filling (such as 95phr), there is between ZD and MH obvious flame retardant synergism.
But, the test data of 10# and 12# carrying out contrast and understands, be the ZD that with the addition of 20phr equally, 140phr fills out
The oxygen index (OI) of the 12# of charge is but significantly lower than the 10# of 95phr loading.Flame retardant synergism meeting between this explanation ZD and MH
Weaken with the increase of the latter's consumption.Its main cause is that the materials such as the magnesium oxide that MH decomposes generation in combustion can press down
System, the formation of destruction carborundum sealing coat, and MH consumption is the biggest, this phenomenon is the most obvious.
Additionally, in the case of MH consumption is constant and ZD addition is gradually increased, the hot strength of system keeps not substantially
Becoming or slightly rise, elongation at break then presents obvious cumulative rule.I.e. ZD is in terms of improving fire proofing mechanical property
Effect under conditions of not affecting hot strength, the elongation at break of material is mainly significantly increased.
Application Example 3
Obtained for embodiment 1 product is added in EVA/LDPE/ATH/MH system, and by its properties and EVA/
LDPE, EVA/LDPE/ATH/MH system contrasts.Sample preparation and mechanics, oxygen index (OI) method of testing and Application Example 1 phase
With；Carbon left calculates, and uses thermogravimetric analyzer to test and calculate, and test temperature is 30 DEG C～600 DEG C, and heating rate 10 DEG C/
min；Cracking resistance is tested, and carries out according to GB/T 2951.6 1997,150 DEG C, 1h.Test result is shown in Table 3.
Table 3
Note: ATH/MH, 120phr in table；ZD, 10phr.
As shown in Table 3, after adding ZD in common flame-proof material system 14#, the hot strength of system improves 13.3%, disconnected
Split percentage elongation and improve 15.8%.This shows that ZD can improve inorganic fire-retarded filler dispersion in matrix resin, increases interface
Intensity, thus material can be made to have good mechanical property.
By 15# Yu 14# contrast it can be seen that after the ZD adding 10phr, the oxygen index (OI) of formula is risen to by 31.8
35.5, carbon left is risen to 10.0% by 6.1%, and both of which improves a lot.This explanation ZD really serves fire-resistant synergistic and makees
With, and achieve the highly effective flame-retardant under low usage amount.
It addition, cracking resistance test shows, although common flame-proof material (14#) can not be tested by cracking resistance, but adds wherein
Just the flame-proof material (15#) that anti-cracking performance is excellent is can get after entering the ZD of 10phr.Therefore, multi-fuactional master-batch ZD can not only
Improve mechanical property and the fire resistance of material, it is also possible to give material with excellent cracking resistance characteristic.
Application Example 4
Obtained for embodiment 2 product and silicone master batch (Wa Ke company of Germany produces) are respectively added to EVA/LLDPE/EVA-
In g-MAH/ATH/MH system, and their properties is contrasted.The consumption of meter EVA/LLDPE/EVA-g-MAH is
100 parts, the consumption of ZD and ATH/MH is listed in table 4.Sample preparation and mechanics, oxygen index (OI) method of testing are identical with Application Example 1,
Torque be use torque rheometer 150 DEG C, measure under conditions of 45rpm, test result is shown in Table 4.
Table 4
Note: in table, the silicone content equivalence of silicone master batch (7.5phr) and ZD (15phr) is equal.
As shown in Table 4, in 95 parts low filling systems, the equal ZD of silicone content (17# formula) and silicone it are separately added into
Master batch (16# formula), the former oxygen index (OI) and elongation at break are obviously higher than the latter.The fire-resistant synergistic effect ratio of this explanation ZD
Silicone master batch is notable, and its in terms of improving Materials Fracture percentage elongation than silicone master batch advantageously.
It addition, be separately added into 5 parts of ZD (19# formula) and 5 parts of silicone master batch (18# formula) in 150 parts high filling systems,
The former processing torque, hot strength and elongation at break is the most all apparently higher than the latter.This shows that ZD makes as processing aid
Used time, the mobile performance of system can be made to improve, thus be effectively reduced processing torque, reduce difficulty of processing, and to a certain degree
On improve the mechanical property of material.
The preparation method of the present invention mainly include material weigh, mix, the step such as banburying and pulverizing.Provided by the present invention
Modified master has following comprehensive function: (1) can be significantly increased the oxygen index (OI) of material, and drippage when improving material combustion is existing
As, fire-resistant synergistic effect is notable；(2) mechanical property of material can be improved, even and if making material when high inorganic fill
Also there is the flexibility under excellent cracking resistance ability and low temperature；(3) can substitute for or part replaces silicone powder, silicone master batch etc.
Processing aid, has price advantage.
Claims (10)
1. the organosilicon multi-fuactional master-batch of a fire-resistant cable material, it is characterised in that according to mass fraction meter, including 90
～the silicone rubber of 120 parts, the ethene-vinyl acetate polymer of 35～60 parts, the Polyolefin Grafted Maleic Anhydride of 35～55 parts, 40
～the organic fatty hydrochlorate of 120 parts, the white carbon of 80～110 parts and the metal-oxide of 10～65 parts.
The organosilicon multi-fuactional master-batch of a kind of fire-resistant cable material the most according to claim 1, it is characterised in that institute
State the polysiloxanes that silicone rubber is the high molecular with reactive functional.
The organosilicon multi-fuactional master-batch of a kind of fire-resistant cable material the most according to claim 1, it is characterised in that institute
Stating vinyl acetate mass content in ethene-vinyl acetate polymer is 12%～40%, and melt index is 2～20g/10min；Silicon
Rubber is methyl phenyl silicone rubber, methyl vinyl silicone rubber, methyl phenyl vinyl silicone rubber, phenylene silicone rubber or benzene
Ether 1,2-ethylidene silicone rubber.
The organosilicon multi-fuactional master-batch of a kind of fire-resistant cable material the most according to claim 1, it is characterised in that institute
State Polyolefin Grafted Maleic Anhydride be maleic anhydride grafted polyethylene, maleic anhydride grafting POE, maleic anhydride inoculated polypropylene,
One or more in maleic anhydride grafting EVA.
The organosilicon multi-fuactional master-batch of a kind of fire-resistant cable material the most according to claim 1, it is characterised in that institute
Stating organic fatty hydrochlorate is one or more in zinc stearate, barium stearate, calcium stearate.
The organosilicon multi-fuactional master-batch of a kind of fire-resistant cable material the most according to claim 1, it is characterised in that institute
State the particle diameter of white carbon less than 3 microns.
The organosilicon multi-fuactional master-batch of a kind of fire-resistant cable material the most according to claim 1, it is characterised in that institute
Stating metal-oxide is one or more in zinc oxide, magnesium oxide, nickel oxide, titanium dioxide, aluminium sesquioxide.
8. the preparation method of the organosilicon multi-fuactional master-batch of a fire-resistant cable material, it is characterised in that include following step
Rapid:
1) weighing: according to mass fraction meter, weighs the silicone rubber of 90～120 parts, the ethene-vinyl acetate polymerization of 35～60 parts
Thing, the Polyolefin Grafted Maleic Anhydride of 35～55 parts, the organic fatty hydrochlorate of 40～120 parts, the white carbon of 80～110 parts and
The metal-oxide of 10～65 parts；
2) material mixing: by super mixer by load weighted metal-oxide, white carbon mix homogeneously, obtain compound A；
3) banburying: load weighted silicone rubber, ethene-vinyl acetate polymer are put into together with Polyolefin Grafted Maleic Anhydride
In banbury, banburying 3～5 minutes within the temperature range of 90 DEG C～110 DEG C；Load weighted organic fatty hydrochlorate is joined close
In refining machine, banburying 5～10 minutes within the temperature range of 100～120 DEG C；Compound A is divided into two parts by weight, adds successively
Enter in banbury, all banburying 5～15 minutes within the temperature range of 110～160 DEG C, the most prepared final fire-retardant electricity add every time after
The organosilicon multi-fuactional master-batch of cable material.
The preparation method of the organosilicon multi-fuactional master-batch of a kind of fire-resistant cable material the most according to claim 8, its
Being characterised by, described silicone rubber is the polysiloxanes of the high molecular with reactive functional；
In described ethene-vinyl acetate polymer, vinyl acetate mass content is 12%～40%, and melt index is 2～20g/
10min；
Described Polyolefin Grafted Maleic Anhydride is maleic anhydride grafted polyethylene, maleic anhydride is grafted POE, maleic anhydride grafting gathers
One or more in propylene, maleic anhydride grafting EVA；
Described organic fatty hydrochlorate is one or more in zinc stearate, barium stearate, calcium stearate；
The particle diameter of described white carbon is less than 3 microns；
Described metal-oxide is one or more in zinc oxide, magnesium oxide, nickel oxide, titanium dioxide, aluminium sesquioxide.
The preparation method of the organosilicon multi-fuactional master-batch of a kind of fire-resistant cable material the most according to claim 8, its
It is characterised by, prepared multi-fuactional master-batch is added and pulverizes to pulverizer, obtain multi-fuactional master-batch powder；
Silicone rubber be methyl phenyl silicone rubber, methyl vinyl silicone rubber, methyl phenyl vinyl silicone rubber, phenylene silicone rubber or
Phenylate 1,2-ethylidene silicone rubber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610596104.2A CN106221220A (en) | 2016-07-26 | 2016-07-26 | A kind of organosilicon multi-fuactional master-batch of fire-resistant cable material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610596104.2A CN106221220A (en) | 2016-07-26 | 2016-07-26 | A kind of organosilicon multi-fuactional master-batch of fire-resistant cable material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106221220A true CN106221220A (en) | 2016-12-14 |
Family
ID=57534267
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610596104.2A Pending CN106221220A (en) | 2016-07-26 | 2016-07-26 | A kind of organosilicon multi-fuactional master-batch of fire-resistant cable material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106221220A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107383572A (en) * | 2017-06-29 | 2017-11-24 | 上海新益电力线路器材有限公司 | A kind of residential housing insulated electric conductor and preparation method thereof |
| CN109251535A (en) * | 2018-09-19 | 2019-01-22 | 铜陵市铜都特种线缆有限公司 | A kind of freeze proof cable cover(ing) of waterproof |
| US10836908B2 (en) | 2018-02-01 | 2020-11-17 | Dow Silicones Corporation | Composition, polymer composite article formed therewith, and method of preparing same |
| CN111944227A (en) * | 2020-08-17 | 2020-11-17 | 东莞市赛美塑胶制品有限公司 | Plastic defoaming master batch and preparation method thereof |
| US11312861B2 (en) | 2019-08-07 | 2022-04-26 | Dow Silicones Corporation | Solid carrier component including a liquid polyorganosiloxane and methods for preparation and use of the solid carrier component |
| US11312862B2 (en) | 2019-08-07 | 2022-04-26 | Dow Silicones Corporation | Solid carrier component including a liquid polydiorganosiloxane and methods for preparation and use of the solid carrier component |
| US11377561B2 (en) | 2019-08-07 | 2022-07-05 | Dow Silicones Corporation | Alkenyl-functional polydiorganosiloxane compositions and methods for use thereof in forming wood plastic composites |
| US11820898B2 (en) | 2019-08-07 | 2023-11-21 | Dow Silicones Corporation | Polydiorganosiloxane compositions and methods for use thereof in forming wood plastic composites |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817952A (en) * | 2010-05-19 | 2010-09-01 | 西安交通大学 | Soft low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof |
| CN102020804A (en) * | 2009-09-15 | 2011-04-20 | 山东安澜高分子材料有限公司 | Thermoplastic crack resistant type low smoke zero halogen flame-retardant polyolefin cable sheath material and preparation method thereof |
-
2016
- 2016-07-26 CN CN201610596104.2A patent/CN106221220A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020804A (en) * | 2009-09-15 | 2011-04-20 | 山东安澜高分子材料有限公司 | Thermoplastic crack resistant type low smoke zero halogen flame-retardant polyolefin cable sheath material and preparation method thereof |
| CN101817952A (en) * | 2010-05-19 | 2010-09-01 | 西安交通大学 | Soft low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 周素蓉等: "有机硅复合物在无卤阻燃电缆料的应用研究", 《塑料工业》 * |
| 王乐等: "一种新型有机硅( ZD)在无卤阻燃电缆料中的应用", 《高分子材料科学与工程》 * |
| 葛涛等: "《功能性塑料母料生产技术》", 30 June 2006, 中国轻工业出版社 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107383572A (en) * | 2017-06-29 | 2017-11-24 | 上海新益电力线路器材有限公司 | A kind of residential housing insulated electric conductor and preparation method thereof |
| CN107383572B (en) * | 2017-06-29 | 2020-06-12 | 临沂沂光电缆有限公司 | Insulated wire for residential building and preparation method thereof |
| US10836908B2 (en) | 2018-02-01 | 2020-11-17 | Dow Silicones Corporation | Composition, polymer composite article formed therewith, and method of preparing same |
| US11884821B2 (en) | 2018-02-01 | 2024-01-30 | Dow Silicones Corporation | Composition, polymer composite article formed therewith, and method of preparing same |
| US11208557B2 (en) | 2018-02-01 | 2021-12-28 | Dow Silicones Corporation | Composition, polymer composite article formed therewith, and method of preparing same |
| CN109251535A (en) * | 2018-09-19 | 2019-01-22 | 铜陵市铜都特种线缆有限公司 | A kind of freeze proof cable cover(ing) of waterproof |
| US11312861B2 (en) | 2019-08-07 | 2022-04-26 | Dow Silicones Corporation | Solid carrier component including a liquid polyorganosiloxane and methods for preparation and use of the solid carrier component |
| US11312862B2 (en) | 2019-08-07 | 2022-04-26 | Dow Silicones Corporation | Solid carrier component including a liquid polydiorganosiloxane and methods for preparation and use of the solid carrier component |
| US11377561B2 (en) | 2019-08-07 | 2022-07-05 | Dow Silicones Corporation | Alkenyl-functional polydiorganosiloxane compositions and methods for use thereof in forming wood plastic composites |
| US11820898B2 (en) | 2019-08-07 | 2023-11-21 | Dow Silicones Corporation | Polydiorganosiloxane compositions and methods for use thereof in forming wood plastic composites |
| US11859086B2 (en) | 2019-08-07 | 2024-01-02 | Dow Silicones Corporation | Polydiorganosiloxane compositions and methods for use thereof in forming wood plastic composites |
| CN111944227B (en) * | 2020-08-17 | 2022-07-15 | 东莞市赛美塑胶制品有限公司 | Plastic defoaming master batch and preparation method thereof |
| CN111944227A (en) * | 2020-08-17 | 2020-11-17 | 东莞市赛美塑胶制品有限公司 | Plastic defoaming master batch and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106221220A (en) | A kind of organosilicon multi-fuactional master-batch of fire-resistant cable material and preparation method thereof | |
| WO2021129216A1 (en) | Pvc cable material and preparation method therefor | |
| CN103275385B (en) | Nuclear power Halogen-free low-smoke flame-retardant cable sheath material and preparation method thereof | |
| CN102898703B (en) | Flame retardant polyolefin cable material and preparation method thereof | |
| CN101735546B (en) | High flame-retardant and high heat-resisting halogen-free expansion type fire-resistant cable material and preparation method thereof | |
| CN102226016B (en) | Nano-mesoporous molecular sieve synergistic intumescent flame-retardant rubber and preparation method thereof | |
| CN103897256B (en) | A kind of 4G optical cable high speed tight jacking of lower shrinkage low smoke and zero halogen and preparation method thereof | |
| CN101712875B (en) | Magnesium hydroxide flame retardant and flame retardant polymer for cables | |
| CN106279956B (en) | A kind of expansion type low-smoke halogen-free high fire-retardance oxygen barrier layer CABLE MATERIALS and preparation method thereof | |
| CN105295379B (en) | One kind can Ceramic silicon rubber composite material and preparation method | |
| CN101323687A (en) | Highly effective flame-retardant environment-protective cross-linking plastic and making process thereof | |
| CN104945728A (en) | Low-smoke zero-halogen flame-retardant sheathing material for ultra-high-voltage cable and preparation method of sheathing material | |
| CN104371199A (en) | Low-smoke halogen-free coal mine electric cable material and preparation method thereof | |
| CN104194145B (en) | A kind of nanometer modified environment-friendly halogen-free polypropylene flame redardant and preparation method thereof | |
| CN102731920A (en) | Compounding flame retardation polystyrene composition and preparation method thereof | |
| CN103073756A (en) | High-ductility, low-smoke, environment-friendly, flame-retardant and oil-proof cable material | |
| CN109233185A (en) | PA/ABS composite material and preparation method | |
| CN114702749A (en) | Flame-retardant polyolefin and preparation method thereof | |
| CN105482349A (en) | High temperature resistant halogen-free flame retardant ABS composition | |
| CN105778417A (en) | Fireproof oxygen-insulation filling material and preparing method thereof | |
| CN107033432A (en) | A kind of room temperature crosslinked with silicane halide-free fireproof composite polyolefine material and preparation method thereof | |
| CN110294890A (en) | A kind of cracking resistance flame-proof cable sheath material and preparation method thereof | |
| CN101323688A (en) | Highly effective flame-retardant environment-protective thermoplastic plastic and making process thereof | |
| CN102731894B (en) | High temperature resistant anti-cracking high-flame retarding irradiation crosslinking low smoke zero halogen cable material and preparation method | |
| CN109161175A (en) | A kind of alloy composite materials of high thermal conductivity high fire-retardance and preparation method thereof and battery case |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161214 |