CN109111594A - Composite flame-retardant agent and preparation method, PP composite material and preparation method, electrical insulation - Google Patents
Composite flame-retardant agent and preparation method, PP composite material and preparation method, electrical insulation Download PDFInfo
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- CN109111594A CN109111594A CN201810848411.4A CN201810848411A CN109111594A CN 109111594 A CN109111594 A CN 109111594A CN 201810848411 A CN201810848411 A CN 201810848411A CN 109111594 A CN109111594 A CN 109111594A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
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- 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
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Abstract
The present invention provides a kind of composite flame-retardant agent and preparation method, PP composite material and preparation method, electrical insulation, is related to polymeric material field.The composite flame-retardant agent preparation method solves the problems, such as that polypropylene material flame retardant property stability difference and fire-retardant long-term effectiveness are poor, which includes: to provide hard-particle powder, calcium carbonate, surfactant and fire retardant；The partial size of hard-particle powder is less than the aperture of calcium carbonate surface hole to be formed less than the partial size of the partial size of calcium carbonate, fire retardant；Hard-particle powder, calcium carbonate, surfactant, fire retardant are mixed, so that hard-particle powder forms hole in calcium carbonate surface, and fire retardant and hard-particle powder are filled into hole；Surfactant with the hydrophilic hydroxyl groups of the calcium carbonate surface after the moisture absorption by being bonded, for preventing agglomerated calcium carbonate.For composite flame-retardant agent and the preparation of PP composite material and electrical insulation including the composite flame-retardant agent.
Description
Technical field
The present invention relates to polymeric material field more particularly to a kind of composite flame-retardant agent and preparation methods, polypropylene composite materials
Material and preparation method, electrical insulation.
Background technique
Requirement of the switch socket to material is: having high intensity, high tenacity, high heat resistance, high fire-retardance, high electrical insulating properties
Energy is equal.Row industry routine scheme of material selection is using flame-proof ABS (acrylonitrile-butadiene-styrene
Copolymer, acrylonitrile-butadiene-styrene copolymer) material, fire retardation PC (Polycarbonate, polycarbonate) material.
With the control of product cost, application of the polypropylene material on socket becomes a kind of trend.
In the prior art, the flame retardant property of material is improved by adding fire retardant into the substrates such as polypropylene, but by
It being unevenly distributed in the substrate in fire retardant, flame retardant property stability is poor, meanwhile, in long-term use process, fire retardant is vulnerable, leads
The flame retardant property of material is caused to be deteriorated.In response to this problem, the flame retardant property of material generally is improved by increasing the dosage of fire retardant,
But increase the dosage of fire retardant, easily lead to the mechanical properties decrease of material.
Summary of the invention
In view of this, to solve problem of the prior art, the embodiment of the present invention provides a kind of composite flame-retardant agent and preparation
Method, PP composite material and preparation method, electrical insulation.The compound resistance obtained using the preparation method of the composite flame-retardant agent
When firing agent and being applied to resin material and prepare, have the advantages that be uniformly distributed in the substrate with it is permanently effective, and will not reduce
The mechanical property of material.
In order to achieve the above objectives, the embodiment of the present invention adopts the following technical scheme that
On the one hand, the embodiment of the invention provides a kind of preparation method of composite flame-retardant agent, the preparation method includes: to mention
For hard-particle powder, calcium carbonate, surfactant and fire retardant；Wherein, the partial size of the hard-particle powder is less than described
The partial size of calcium carbonate, the fire retardant partial size be less than the aperture of calcium carbonate surface hole to be formed；By the hard
Particle powder, the calcium carbonate, the surfactant, the fire retardant are mixed, so that the hard particles powder
End forms described hole in the calcium carbonate surface, and the fire retardant and the hard-particle powder is made to be filled into the hole
In hole；Wherein, the surfactant with the hydrophilic hydroxyl groups of the calcium carbonate surface after the moisture absorption by being bonded, for preventing
State agglomerated calcium carbonate.
Optionally, the preparation method of the composite flame-retardant agent, the partial size of the hard-particle powder are 20-50nm；Institute
The partial size for stating calcium carbonate is 80-400 μm；The partial size of the fire retardant is 20-50nm；The revolving speed of the mixing is 20000-
30000r/min, mixing time 25-30min；The aperture for the described hole that the calcium carbonate surface is formed is 200-400nm.
Optionally, the preparation method of the composite flame-retardant agent, the hard-particle powder include glass particle powder.
Optionally, the preparation method of the composite flame-retardant agent, the hard-particle powder, the calcium carbonate, the table
Face activating agent, the fire retardant mass parts be respectively 2-5 parts, 10-20 parts, 0.01-0.04 parts, 8-15 parts.
Optionally, the preparation method of the composite flame-retardant agent, the surfactant include Aluminate and/or metatitanic acid
Ester, and/or, the fire retardant includes triphenyl phosphate and/or ammonium polyphosphate.
On the other hand, the embodiment of the invention also provides a kind of composite flame-retardant agent, the component of the composite flame-retardant agent includes:
Hard-particle powder, surface have calcium carbonate, surfactant and the fire retardant of hole；Wherein, the hard-particle powder
Partial size is less than the aperture of described hole, the fire retardant and hard less than the partial size of the calcium carbonate, the partial size of the fire retardant
Particle powder is filled in described hole；The hydrophilic hydroxyl groups key of the calcium carbonate surface after the surfactant and the moisture absorption
It closes.
Optionally, the composite flame-retardant agent, the partial size of the hard-particle powder are 20-50nm；The calcium carbonate
Partial size is 80-400 μm, the aperture of described hole is 200-400nm；The partial size of the fire retardant is 20-50nm.
Optionally, the composite flame-retardant agent, the hard-particle powder include glass particle powder.
Optionally, the composite flame-retardant agent, the hard-particle powder, the calcium carbonate, the surfactant, institute
The mass parts for stating fire retardant are respectively 2-5 parts, 10-20 parts, 0.01-0.04 parts, 8-15 parts.
Optionally, the composite flame-retardant agent, the surfactant include Aluminate and/or titanate esters, and/or, institute
Stating fire retardant includes triphenyl phosphate and/or ammonium polyphosphate.
Another further aspect, the embodiment of the invention also provides a kind of preparation method of PP composite material, the preparation sides
Method includes: to mix polypropylene, toughener, composite flame-retardant agent as described above, antioxidant, coupling agent, anti-copper aging agent
It is even, form mixture；Plastics processing, cooling treatment, pelletizing processing are successively carried out to the mixture, form polypropylene composite materials material
Material.
Another further aspect, the embodiment of the invention also provides a kind of PP composite material, the PP composite material groups
Dividing includes: polypropylene, toughener, composite flame-retardant agent as described above, antioxidant, coupling agent, anti-copper aging agent.
Optionally, the PP composite material, it is the polypropylene, the toughener, the composite flame-retardant agent, described
Antioxidant, the coupling agent, the anti-copper aging agent mass parts be respectively 55 parts, 10-15 parts, 20-40 parts, 0.1-1.2 parts,
1-3 parts, 0.1-1.2 parts.
Optionally, the PP composite material, the polypropylene include copolymer polypropylene and/or homopolypropylene；
The toughener includes the high polymer of ethylene and octene；The antioxidant includes four [β-(3,5- di-tert-butyl-hydroxy phenyl)
Propionic acid] pentaerythritol ester and/or bis- (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites；The coupling agent includes ethylene
Ethyl triethoxy silicane alkane；The anti-copper aging agent includes Hinered phenols non-polluting copper resistant agent.
Another further aspect, the embodiment of the invention also provides a kind of electrical insulations, and the electrical insulation is by as described above
PP composite material is made.
Optionally, the electrical insulation, the electrical insulation include: the shell or converter shell of socket.
Based on this, the preparation method of above-mentioned composite flame-retardant agent provided in an embodiment of the present invention, by by hard-particle powder,
Calcium carbonate, surfactant, the stirring of fire retardant mixed at high speed, hard-particle powder high-speed impact calcium carbonate, in calcium carbonate surface
Hole is formed, with the progress of stirring, fire retardant and hard-particle powder are filled into these holes, surfactant and the moisture absorption
The hydrophilic hydroxyl groups of calcium carbonate surface afterwards are bonded, and obtain above-mentioned composite flame-retardant agent.
The suitable hard-particle powder fast ram calcium carbonate of partial size, is formed on its surface the suitable micro hole of pore diameter range
Hole, so that the calcium carbonate can be used as the carrier of fire retardant dispersion, so that the smaller fire retardant of partial size and hard-particle powder are filled out
It fills in the small hole of calcium carbonate.In the small hole of calcium carbonate, hard-particle powder can be blocked fire retardant,
Prevent fire retardant from overflowing from the small hole of calcium carbonate, so that the Long-Term Properties of fire retardant are improved, so that the material after aging
The flame retardant property of material is not in be decreased obviously.
In addition, since bonding action, enhancing occur for the hydrophilic hydroxyl groups of the calcium carbonate surface after surfactant and micro- moisture absorption
The affinity of inorganic assistant calcium carbonate and organic resin matrix, prevents agglomerated calcium carbonate, so that composite flame-retardant agent is applied to tree
When prepared by rouge material, can equably it disperse in resin matrix, so that the flame retardant property of obtained material significantly improves, thus
Reach when preparing resin material, only need to can reach and be evenly distributed with less amount of above-mentioned composite flame-retardant agent, flame retardant property is long
The high effect of phase stability.
It, can be with tree when above-mentioned composite flame-retardant agent is applied to resin material preparation also, due to the presence of calcium carbonate micropore
Aliphatic radical material generates riveting effect, the mechanical property of material will not because of calcium carbonate builder addition and be greatly lowered.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is a kind of composite flame-retardant agent preparation method flow diagram provided in an embodiment of the present invention.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
As shown in Figure 1, the embodiment of the invention provides a kind of preparation method of composite flame-retardant agent, which includes:
Step S101, hard-particle powder, calcium carbonate, surfactant and fire retardant are provided；Wherein, hard-particle powder
Partial size be less than the partial size of calcium carbonate, the partial size of fire retardant is less than the aperture of calcium carbonate surface hole to be formed；
Step S102, hard-particle powder, calcium carbonate, surfactant, fire retardant are mixed, so that hard
Particle powder forms hole in calcium carbonate surface, and fire retardant and fire retardant are filled into hole；Wherein, surfactant
By being bonded with the hydrophilic hydroxyl groups of the calcium carbonate surface after the moisture absorption, for preventing agglomerated calcium carbonate.
It should be noted that the structure of first, calcium carbonate is of a relatively loose, it is easy under the fast ram of hard-particle powder
Form hole.The hardness of hard-particle powder is for calcium carbonate, as long as hardness, which can satisfy, is hitting carbonic acid
When calcium, hole can be formed in calcium carbonate surface.
In view of composite flame-retardant agent made from the preparation method is usually applied in resin, calcium carbonate is selected also as it has
Have the advantages that good dispersion, with resin compatible is good, slightly hygroscopicity, from a wealth of sources, cheap, and it is being applied to modeling
Material, Rubber Industry when show significantly enhance, toughening effect, be often used as polyamide, polycarbonate, thermoplastic polyester,
The reinforced modifier and dispersing agent of the resins such as ABS, PP (Polypropylene, polypropylene).
The second, hard-particle powder, calcium carbonate, surfactant, fire retardant are mixed, so that hard particles
Powder forms hole in calcium carbonate surface, and in quick mixing process, hard-particle powder hits calcium carbonate many times, makes
It obtains calcium carbonate surface and forms small hole.
Third, hard-particle powder hit calcium carbonate, so that calcium carbonate surface forms small hole, this allows for hard
The partial size of particle powder need to be smaller than the partial size of calcium carbonate, not smaller than the partial size of calcium carbonate to the partial size of hard-particle powder more herein
It is defined less, as long as hard-particle powder hits calcium carbonate, so that calcium carbonate surface forms small hole.Quick
In whipping process, many a hard particles hit calcium carbonate, this allows for calcium carbonate surface and forms the aperture of hole greater than hard
The partial size of particle.With the progress of stirring, since the partial size of fire retardant and hard-particle powder is less than the hole of calcium carbonate surface
Aperture, fire retardant and hard-particle powder are filled into the small hole of calcium carbonate surface.
Exemplary, above-mentioned mixing can be completed in high-speed mixer.
4th, calcium carbonate has micro- moisture absorption, and hydrophilic hydroxyl groups are distributed in the calcium carbonate surface after micro- moisture absorption.Surfactant
By the way that bonding action occurs with the hydrophilic hydroxyl groups, the compatibility of calcium carbonate Yu toughener and resin (such as PP) can be improved, made
Composite flame-retardant agent made from the above method is obtained when being used to prepare resin material, the reunion of calcium carbonate can be effectively prevent, improves carbon
Dispersibility of the sour calcium in resin.
Based on this, the preparation method of above-mentioned composite flame-retardant agent provided in an embodiment of the present invention, by by hard-particle powder,
Calcium carbonate, surfactant, the stirring of fire retardant mixed at high speed, hard-particle powder high-speed impact calcium carbonate, in calcium carbonate surface
Hole is formed, with the progress of stirring, fire retardant and hard-particle powder are filled into these holes, surfactant and the moisture absorption
The hydrophilic hydroxyl groups of calcium carbonate surface afterwards are bonded, and obtain above-mentioned composite flame-retardant agent.
The suitable hard-particle powder fast ram calcium carbonate of partial size, is formed on its surface the suitable micro hole of pore diameter range
Hole, so that the calcium carbonate can be used as the carrier of fire retardant dispersion, so that the smaller fire retardant of partial size and hard-particle powder are filled out
It fills in the small hole of calcium carbonate.In the small hole of calcium carbonate, hard-particle powder can be blocked fire retardant,
Prevent fire retardant from overflowing from the small hole of calcium carbonate, so that the Long-Term Properties of fire retardant are improved, so that the material after aging
The flame retardant property of material is not in be decreased obviously.
In addition, since bonding action, enhancing occur for the hydrophilic hydroxyl groups of the calcium carbonate surface after surfactant and micro- moisture absorption
The affinity of inorganic assistant calcium carbonate and organic resin matrix, prevents agglomerated calcium carbonate, so that composite flame-retardant agent is applied to tree
When prepared by rouge material, can equably it disperse in resin matrix.When preparing resin material, by the composite flame-retardant agent and other
During component mixes, only less amount of composite flame-retardant agent, which need to be added, can reach the effect being evenly distributed, so that obtain
The flame retardant property of material significantly improves.
It, can be with tree when above-mentioned composite flame-retardant agent is applied to resin material preparation also, due to the presence of calcium carbonate micropore
Aliphatic radical material generates riveting effect, the mechanical property of material will not because of calcium carbonate builder addition and be greatly lowered.
Exemplary, the partial size of hard-particle powder is 20-50nm, and the partial size of calcium carbonate is 80-400 μm, the grain of fire retardant
Diameter is 20-50nm, and the revolving speed of mixing is 20000-30000r/min, mixing time 25-30min, calcium carbonate surface shape
At hole aperture be 200-400nm.
Under the comprehensive function of above-mentioned parameters condition, so that calcium carbonate surface forms the hole that aperture is 200-400nm
Hole.
When the hole that calcium carbonate surface is formed is excessive, fire retardant is easy to cause to overflow from hole；Work as calcium carbonate surface
When the hole of formation is too small, the fire retardant for being easy to cause calcium carbonate carrier to carry is very little, prevent fire retardant is from resin base material
In be uniformly distributed.
It is measured (see below experiment) by experiment, it is preferable that surface, which is formed with the calcium carbonate that aperture is 200-400nm hole,
Fire-retardant agent carrier, enough fire retardants can be carried and be evenly distributed in resin base material, and fire retardant be not easy from hole overflow
Out.
In addition, the too big calcium carbonate of partial size is added in resin base material, it is easy to cause the mechanical properties decrease of resin base material, grain
The too small calcium carbonate of diameter cannot carry enough fire retardants again, cannot effectively improve the flame retardant property of resin base material.Calcium carbonate can
The calcium carbonate that the calcium carbonate that selection partial size is 80-400 μm, preferably partial size are 100-150 μm.
Exemplary, hard-particle powder includes glass powder.
Glass powder is inorganic stabilized hard particle powder, and it is PbO, SiO that raw material is used in production2、TiO2Equal electron levels raw material
After mixing, then high temperature carries out solid phase reaction, and the glass isotropic body of the disordered structure of formation there is chemical property to stablize, low bulk
The advantages that coefficient, partial size be small, good dispersion, surface also have good affinity after improving.
Further, the preparation method of above-mentioned composite flame-retardant agent, the mass parts that each component is added are respectively as follows: hard particles powder
2-5 parts last, 10-20 parts of calcium carbonate, 0.01-0.04 parts of surfactant, 8-15 parts of fire retardant.
Exemplary, surfactant includes Aluminate and/or titanate esters；Fire retardant includes triphenyl phosphate and/or poly- phosphorus
Sour ammonium.
Wherein, for surfactant, Aluminate have it is applied widely, it is easy to use without diluent, it is cheap
The advantages that；Through Aluminate activation modification treated inorganic particle (such as the calcium carbonate in the present invention) except with stable excellent of quality
Point is outer, also has many advantages, such as that color is shallow, nontoxic, taste is small.
It is therefore preferred that above-mentioned surfactant is Aluminate.
Wherein, for fire retardant, triphenyl phosphate is white odorless or powder crystallization, non-combustible, volatility is low, is had
The advantages that transparency, flexibility, toughness, plasticising anti-flammability and excellent photostability.Due to the current process polymerisation of ammonium polyphosphate
Degree is smaller, so having biggish hygroscopicity, and very big to the Effect on Mechanical Properties of engineering plastics.
It is therefore preferred that above-mentioned fire retardant is triphenyl phosphate.
On the basis of the above, the embodiment of the invention also provides a kind of composite flame-retardant agent, the group subpackages of the composite flame-retardant agent
Include: hard-particle powder, surface have calcium carbonate, surfactant and the fire retardant of hole, wherein the grain of hard-particle powder
Diameter is less than the partial size of the partial size of calcium carbonate, fire retardant less than the aperture of hole, and fire retardant and hard-particle powder are filled in hole
In；Surfactant is bonded with the hydrophilic hydroxyl groups of the calcium carbonate surface after the moisture absorption.
Wherein, the partial size of hard-particle powder can be 20-50nm, and the partial size of calcium carbonate can be 80-400 μm, hole
Aperture can be 200-400nm, the partial size of fire retardant is 20-50nm.
Further, the partial size of calcium carbonate can be 100-150 μm.
Exemplary, hard-particle powder includes glass powder.
Further, hard-particle powder, calcium carbonate, surfactant, fire retardant mass parts be respectively 2-5 parts, 10-
20 parts, 0.01-0.04 parts, 8-15 parts.
Exemplary, surfactant includes Aluminate and/or titanate esters；Fire retardant includes triphenyl phosphate and/or poly- phosphorus
Sour ammonium.
On the basis of the above, the embodiment of the invention also provides a kind of preparation method of PP composite material, the preparations
Method includes:
Polypropylene, toughener, above-mentioned composite flame-retardant agent, antioxidant, coupling agent, anti-copper aging agent are uniformly mixed, shape
At mixture；
Plastics processing, cooling treatment, pelletizing processing are successively carried out to mixture, form PP composite material.
It should be noted that first, toughener, which refers to, can increase the flexible substance of adhesive film layer.Toughener can lower
Adhesive brittleness increases toughness, and does not influence other main performances of adhesive.
The second, coupling agent is usually also referred to as compatilizer, and the combination between composite flame-retardant agent and toughener, PP can be improved
Power.
Third, antioxidant can delay or inhibit the progress of polymer oxidation process, to prevent the aging of polymer and prolong
Its long service life.
4th, in view of PP composite material made from above-mentioned preparation method can be used to make electrical insulation (such as
Jack housing), it is often necessary to it is directly contacted with metal, metal ion has catalysis aging action, institute to PP composite material
With above-mentioned preparation method is also added into anti-copper aging agent, for inhibiting heavy metal to be passivated, inhibits (copper) metal ion to resin base
The catalysis aging action of material.
Based on this, due to joined above-mentioned composite flame-retardant agent, PP composite material tool obtained during the preparation process
There are high fire-retardance grade, high tenacity, high heat distortion temperature, low linear expansion coefficient, material injection size after molding is steady
It is qualitative good.
Further, polypropylene, toughener, composite flame-retardant agent, antioxygen is added in the preparation method of the PP composite material
Agent, coupling agent, anti-copper aging agent mass parts be respectively 55 parts, 10-15 parts, 20-40 parts, 0.1-1.2 parts, 1-3 parts, 0.1-
1.2 part.
Exemplary, polypropylene includes copolymer polypropylene and/or homopolypropylene.
Since copolymer polypropylene is cheap and easy to get, polypropylene is preferably copolymer polypropylene, melt index 14-40g/
10min。
Toughener includes the high polymer of ethylene and octene.
It should be noted that the high polymer of ethylene and octene is commonly referred to as POE.
Antioxidant includes four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and/or bis- (2,4- bis-
Tert-butyl-phenyl) pentaerythritol diphosphites.
It should be noted that the adopted name of four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters
For antioxidant 1010, it is phenolic antioxidant, is one of outstanding kind of current antioxidant, has brilliance to polypropylene, polyethylene
Antioxygenic property can effectively extend the service life of product.
Bis- (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites adopted names are antioxidant 626, are a kind of efficient
Auxiliary type antioxidant, there is yellowing-resistant, it is often anti-with the phenols master such as antioxidant 1010 the features such as high transparency, low volatility
Oxygen agent is used in combination.
When antioxidant selection antioxidant is 1010 and the mixture of antioxidant 626, wherein based on antioxidant 1010, resist
Supplemented by oxygen agent 626.Preferably, mass ratio 1.7-1.9:1 further can effectively extend the service life of product and delay to make
The flavescence time limit of product.
Exemplary, coupling agent includes vinyltriethoxysilane (normally referred to as YDH-151 in industry), can be effective
Improve the binding force between composite flame-retardant agent and toughener, resin (such as PP).
Anti- copper aging agent includes Hinered phenols non-polluting copper resistant agent.
Hinered phenols non-polluting copper resistant agent has the function of that heavy metal passivation inhibits, inhibits the effect of (copper) metal ion,
It is a kind of efficient copper deactivator.
On the basis of the above, the embodiment of the invention also provides a kind of PP composite material, the PP composite materials
Component includes: polypropylene, toughener, above-mentioned composite flame-retardant agent, antioxidant, coupling agent, anti-copper aging agent.
Further, polypropylene, toughener, composite flame-retardant agent, antioxidant, coupling agent, anti-copper aging agent mass parts point
It Wei not be 55 parts, 10-15 parts, 20-40 parts, 0.1-1.2 parts, 1-3 parts, 0.1-1.2 parts.
Exemplary, polypropylene includes copolymer polypropylene and/or homopolypropylene, and toughener includes that the height of ethylene and octene is poly-
Object, antioxidant include four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and/or bis- (2,4- bis- tertiary fourths
Base phenyl) pentaerythritol diphosphites；Coupling agent includes vinyltriethoxysilane；Anti- copper aging agent includes Hinered phenols
Non-polluting copper resistant agent.
On the basis of the above, the embodiment of the invention also provides a kind of electrical insulations, and the electrical insulation is by above-mentioned polypropylene
Composite material is made.
The electrical insulation flame retardant property stability is high, and in long-term use process, fire retardant is not also vulnerable, mechanical property phase
Existing electrical insulation is not also declined.
Exemplary, which includes: the shell or converter shell of socket.
Below with reference to experiment, the present invention will be further described, but embodiment used be only intended to illustrate the present invention without
It is the limitation present invention.It is only illustrated by taking materials described below as an example below.
The material of selection is as follows:
Hard-particle powder selects glass powder；
Surfactant selects Aluminate；
Fire retardant selects triphenyl phosphate；
Polypropylene selects copolymer polypropylene；
The high polymer of toughener selection ethylene and octene；
It is the mixture of 1010 and antioxidant 626 that antioxidant, which selects antioxidant, wherein based on antioxidant 1010, antioxygen
Supplemented by agent 626, mass ratio 1.7-1.9:1；
Coupling agent selects YDH-151 (vinyltriethoxysilane)；
Hinered phenols non-polluting copper resistant agent is selected in anti-copper aging agent.
This experiment has done 9 experimental groups using above-mentioned material, wherein 5 experimental groups are comparative examples, respectively comparative example 1-
5,4 experimental groups are embodiments, respectively embodiment 1-4.
The formula for raw stock of comparative example 1-5 and embodiment 1-4 are as follows:
The formula for raw stock table of table 1-1. comparative example 1-7
The formula for raw stock table of table 1-2. embodiment 1-8
Note: the unit of aperture and partial size is μm in table 1-1 and table 1-2.
It should be noted that in table 1 above, since comparative example 1, comparative example 3 are into embodiment 4, being added has glass
Powder, so as to knock out hole in calcium carbonate surface in quick whipping process；And that glass is not added in comparative example 2
Powder, therefore calcium carbonate surface not will form hole.Comparative example 1, comparative example 3 to be added into embodiment 4 convenient for distinguishing herein
Calcium carbonate is known as " micropore calcium carbonate ", and the calcium carbonate being added in comparative example 2 is known as " ordinary calcium carbonate ".
The above-mentioned Nano glass powder of formula ratio each in table 1, calcium carbonate, surfactant, fire retardant are mixed, obtained
To composite flame-retardant agent.Specific preparation method is seen above, and details are not described herein again.
The above-mentioned polypropylene of formula ratio each in table 1, toughener, composite flame-retardant agent, antioxidant, coupling agent, anti-copper is old
Agent is uniformly mixed, and forms mixture；Plastics processing, cooling treatment, pelletizing processing are successively carried out to mixture, form polypropylene
Composite material.
The PP composite material injected sample that will be obtained.
The equipment that this experiment plastics processing process uses is double screw extruder, and the draw ratio of extruder screw is 37-45,
Temperature of each section and revolving speed are as follows:
Each workshop section's parameter list of 2. double screw extruder of table
Material injection sample is made in above-mentioned each comparative example and each embodiment to test according to following standard, it is as a result as follows
Table:
Material injection sample tests table is made in table 3. comparative example 1-7 and embodiment 1-8
Note: ISO (International Organization for Standardization, International standardization group
It knits).
ISO 527, ISO 178, ISO 180, ISO 75, ISO 11359 are respectively plastic tensile performance, plastics bendability
Energy, plastics notched impact properties, plastics load deformation temperature, coefficient linear thermal expansion and glass transition temperature measurement mark
It is quasi-.
UL94:Test for Flammability of Plastic Materials for Parts in Devices
And Appliances (equipment and device component plastic material combustion testing).
UL94 includes multiple fire-protection ratings, wherein HB grades refer to that Horizontal Burning Test (survey by horizontal firing
Examination) grade, V0, V1, V2 grades of three grades for referring to Vertical Burning Test (vertical burn test).
By table 3 it follows that
In comparative example 1, due to not having to add toughener POE ingredient, the notch impact strength of material is low, and material is tough
Property is poor.
In comparative example 2, although being added to ordinary calcium carbonate, produced without being mixed to hit by Nano glass powder
Raw micropore, therefore lack micropore as the carrier for carrying fire retardant, lead to the bad dispersibility of microcosmic upper fire retardant in the material, it is macro
The poor flame retardant properties of material in sight, only UL94V1 rank, and Flame Retardancy can be obvious after 100 DEG C of agings in 14 days for material
Decline, falls to UL94HB rank.
In comparative example 3, since Nano glass powder partial size is small, with hit the micro- of generation in calcium carbonate whipping process
Hole aperture is smaller, leads to bad dispersibility of the microcosmic upper fire retardant in calcium carbonate micropore, and then be presented as fire retardant in the material
Bad dispersibility, the macroscopically poor flame retardant properties of material, only UL94V1 rank, and material material after 100 DEG C of agings in 14 days
Material flame retardant property is decreased obviously, and falls to UL 94HB rank.
In comparative example 4, since Nano glass powder partial size is big, with hit the micro- of generation in calcium carbonate whipping process
Hole aperture is larger, to destroy the main structure of calcium carbonate microparticle, calcium carbonate is caused to die down the humidification of material, so that
Testing of materials notch impact strength only has 16KJ/m2.
In comparative example 5, due to there is no addition surfactant, thus while fire retardant can be in calcium carbonate by nanometer glass
It is uniformly distributed in the micropore that glass powder is hit, but is the absence of the key of the calcium carbonate surface hydrophilic hydroxyl groups after surfactant and micro- moisture absorption
Cooperation is used, and microcosmic upper calcium carbonate is caused to be reunited in the material, and dispersion is uneven, macroscopically the poor flame retardant properties of material, only
There is UL94V2 rank, and material Flame Retardancy after 100 DEG C of agings in 14 days can be decreased obviously, and fall to UL 94HB rank.
In comparative example 6, since calcium carbonate partial size is small, it is unfavorable for Nano glass powder shock, the effect for forming micropore is poor.It leads
Bad dispersibility of the microcosmic upper fire retardant in calcium carbonate micropore is caused, and then is presented as the bad dispersibility of fire retardant in the material, it is macro
The poor flame retardant properties of material in sight, only UL94V1 rank, and Flame Retardancy can be obvious after 100 DEG C of agings in 14 days for material
Decline, falls to UL 94HB rank.
In comparative example 7, since calcium carbonate partial size is big, it is evenly dispersed in resin to be unfavorable for calcium carbonate.Material is more crisp,
So that testing of materials notch impact strength only has 18.8KJ/m2.
In embodiment 1-8, Nano glass powder, calcium carbonate, surfactant, fire retardant are obtained compound by reasonable process
Fire retardant, since the partial size of Nano glass powder is suitable, so that the suitable micropore of pore diameter range that calcium carbonate surface is formed after hitting
The carrier that can preferably disperse as fire retardant, so that fire retardant is evenly dispersed in calcium carbonate micropore.
In addition, enhancing inorganic assistant calcium carbonate and organic resin due to the bonding action of surfactant and calcium carbonate
The affinity of matrix, composite flame-retardant agent can uniformly disperse in resin matrix, and the Flame Retardancy enabled is obvious
It is promoted, can achieve UL94 1.0mm V0 grade.
In addition, since Nano glass powder can block the micropore of calcium carbonate, so that the long-time service of fire retardant
It can improve, material Flame Retardancy after 100 DEG C of agings in 14 days can be not in be decreased obviously.
Further, since the linear expansion coefficient of material obtained is small, so that material injection good stability of the dimension after molding.
Simultaneously as the presence of calcium carbonate micropore, riveting effect can be generated with resin base material, so that the mechanical property of material will not be because
For calcium carbonate builder addition and be greatly lowered.
Therefore, material made from embodiment 1-4 has high fire-retardance grade, high tenacity, high heat distortion temperature, low linear expansion
The advantages that coefficient.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (16)
1. a kind of preparation method of composite flame-retardant agent, which is characterized in that the preparation method includes:
Hard-particle powder, calcium carbonate, surfactant and fire retardant are provided；Wherein, the partial size of the hard-particle powder is small
It is less than the aperture of calcium carbonate surface hole to be formed in the partial size of the calcium carbonate, the partial size of the fire retardant；
The hard-particle powder, the calcium carbonate, the surfactant, the fire retardant are mixed, so that
The hard-particle powder forms described hole in the calcium carbonate surface, and makes the fire retardant and the hard particles powder
End is filled into described hole；
Wherein, the surfactant with the hydrophilic hydroxyl groups of the calcium carbonate surface after the moisture absorption by being bonded, for preventing
State agglomerated calcium carbonate.
2. the preparation method of composite flame-retardant agent according to claim 1, which is characterized in that
The partial size of the hard-particle powder is 20-50nm；
The partial size of the calcium carbonate is 80-400 μm；
The partial size of the fire retardant is 20-50nm；
The revolving speed of the mixing is 20000-30000r/min, mixing time 25-30min；
The aperture for the described hole that the calcium carbonate surface is formed is 200-400nm.
3. the preparation method of composite flame-retardant agent according to claim 2, which is characterized in that
The hard-particle powder includes glass powder.
4. the preparation method of composite flame-retardant agent according to claim 1, which is characterized in that
The hard-particle powder, the calcium carbonate, the surfactant, the fire retardant mass parts be respectively 2-5 parts,
10-20 parts, 0.01-0.04 parts, 8-15 parts.
5. the preparation method of composite flame-retardant agent according to claim 4, which is characterized in that
The surfactant includes Aluminate and/or titanate esters,
And/or
The fire retardant includes triphenyl phosphate and/or ammonium polyphosphate.
6. a kind of composite flame-retardant agent, which is characterized in that the component of the composite flame-retardant agent includes:
Hard-particle powder, surface have calcium carbonate, surfactant and the fire retardant of hole；
Wherein, described in the partial size of the hard-particle powder is less than the partial size of the calcium carbonate, the partial size of the fire retardant is less than
The aperture of hole, the fire retardant and hard-particle powder are filled in described hole；
The surfactant is bonded with the hydrophilic hydroxyl groups of the calcium carbonate surface after the moisture absorption.
7. composite flame-retardant agent according to claim 6, which is characterized in that
The partial size of the hard-particle powder is 20-50nm；
The partial size of the calcium carbonate is 80-400 μm, the aperture of described hole is 200-400nm；
The partial size of the fire retardant is 20-50nm.
8. composite flame-retardant agent according to claim 7, which is characterized in that the hard-particle powder includes glass powder.
9. composite flame-retardant agent according to claim 6, which is characterized in that
The hard-particle powder, the calcium carbonate, the surfactant, the fire retardant mass parts be respectively 2-5 parts,
10-20 parts, 0.01-0.04 parts, 8-15 parts.
10. composite flame-retardant agent according to claim 9, which is characterized in that the surfactant include Aluminate and/or
Titanate esters,
And/or
The fire retardant includes triphenyl phosphate and/or ammonium polyphosphate.
11. a kind of preparation method of PP composite material, which is characterized in that the preparation method includes:
Polypropylene, toughener, such as described in any item composite flame-retardant agents of claim 6-10, antioxidant, coupling agent, anti-copper is old
Agent is uniformly mixed, and forms mixture；
Plastics processing, cooling treatment, pelletizing processing are successively carried out to the mixture, form PP composite material.
12. a kind of PP composite material, which is characterized in that the PP composite material component includes: polypropylene, toughening
Agent, such as described in any item composite flame-retardant agents of claim 6-10, antioxidant, coupling agent, anti-copper aging agent.
13. PP composite material according to claim 12, which is characterized in that
The polypropylene, the toughener, the composite flame-retardant agent, the antioxidant, the coupling agent, the anti-copper aging agent
Mass parts be respectively 55 parts, 10-15 parts, 20-40 parts, 0.1-1.2 parts, 1-3 parts, 0.1-1.2 parts.
14. PP composite material according to claim 13, which is characterized in that
The polypropylene includes copolymer polypropylene and/or homopolypropylene；
The toughener includes the high polymer of ethylene and octene；
The antioxidant includes four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and/or bis- (2,4- bis-
Tert-butyl-phenyl) pentaerythritol diphosphites；
The coupling agent includes vinyltriethoxysilane；
The anti-copper aging agent includes Hinered phenols non-polluting copper resistant agent.
15. a kind of electrical insulation, which is characterized in that the electrical insulation is by such as claim 12-14 described in any item poly- third
Alkene composite material is made.
16. electrical insulation according to claim 15, which is characterized in that the electrical insulation includes: the shell of socket, wall
Wall switch panel or electronic equipment casing.
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Cited By (1)
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| CN112500634A (en) * | 2020-10-26 | 2021-03-16 | 江阴中达软塑新材料股份有限公司 | Biaxially oriented polypropylene heat-sealing film and preparation process thereof |
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| JP2001220463A (en) * | 2000-02-09 | 2001-08-14 | Ishizuka Glass Co Ltd | Method for producing composite composition for imparting flame retardance and composite composition for imparting flame retardance |
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