CN109337185A - A method of preparing halogen-free flameproof EVA/PA6 polymer alloy - Google Patents

A method of preparing halogen-free flameproof EVA/PA6 polymer alloy Download PDF

Info

Publication number
CN109337185A
CN109337185A CN201811073522.9A CN201811073522A CN109337185A CN 109337185 A CN109337185 A CN 109337185A CN 201811073522 A CN201811073522 A CN 201811073522A CN 109337185 A CN109337185 A CN 109337185A
Authority
CN
China
Prior art keywords
eva
drying
parts
halogen
free flameproof
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
Application number
CN201811073522.9A
Other languages
Chinese (zh)
Inventor
高喜平
陆昶
姚大虎
余志强
赫玉欣
张玉清
郭小熙
齐晨晨
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henan University of Science and Technology
Original Assignee
Henan University of Science and Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henan University of Science and Technology filed Critical Henan University of Science and Technology
Priority to CN201811073522.9A priority Critical patent/CN109337185A/en
Publication of CN109337185A publication Critical patent/CN109337185A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
    • C08K2003/323—Ammonium polyphosphate
    • 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
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention provides a kind of method for preparing halogen-free flameproof EVA/PA6 polymer alloy, halogen-free flameproof EVA/PA6 polymer alloy is grouped as by each group of following mass fraction: EVA50 ~ 70 part, 10 ~ 30 parts of PA6,10 ~ 30 parts of expanding fire retardant；The preparation method of halogen-free flameproof EVA/PA6 polymer, the following steps are included: 1) be dried in vacuo respectively to EVA and PA6,2) EVA and PA6 in step 1) after drying is taken to be put into high-speed mixer and uniformly mix, then 10 ~ 30 parts of expanding fire retardant are added into high-speed mixer again uniformly to be mixed, obtain mixed material；3) mixed material in step 2 is put into melt blending in double screw extruder, then it is granulated by extruder, obtain halogen-free flameproof EVA/PA6 polymer, the method that the present invention uses melt-processed to be blended, ammonium polyphosphate and the pentaerythrite composition Intumescent Retardant System with good char forming ability are added in EVA/PA6 polymer, a kind of EVA/PA6 polymer alloy with good flame-retardance is prepared.

Description

A method of preparing halogen-free flameproof EVA/PA6 polymer alloy
Technical field
The present invention relates to the technical field for preparing Halogenless fire retarded polymer more particularly to a kind of prepare halogen-free flameproof EVA/ The method of PA6 polymer alloy.
Background technique
Ethylene-vinyl acetate (EVA) is to be copolymerized by ethylene and vinylacetate according to different ratios, EVA with Polyethylene is compared, and due to introducing polarity side group on strand, the degree of branching of polymer is improved, to reduce polymer point The regularity of subchain, thereby reduces the crystallinity of polymer, the variations of these structures is so that EVA has good elasticity, soft Toughness, cementability, low-temperature flexibility, stress cracking resistance, weatherability and chemical resistance etc., meanwhile, also reduce EVA material Tensile strength, hardness, rigidity etc.；And EVA molding easy to process, it is suitable for a variety of processing methods such as extrusion, injection, thermoforming, Keep its application field extremely extensive, be mainly used in wire and cable, foam plastic product, sealing element, medical catheter, insulation it is thin The fields such as the modifying agent of film, adhesive and other resins.
Although EVA toughness is preferable, mechanical strength is lower, not wear-resisting, and which has limited its further applications.Using existing Polymer be blended, the performance advantage of different polymer can be made complementary, so that original copolymer is obtained performance improvement, to improve The performance of material in a certain respect.Nylon 6(PA6) it is a kind of thermoplastic engineering plastic haveing excellent performance, it has excellent mechanics Performance, preferable electrical property and wear-resisting, oil resistant, solvent resistant, self-lubricating, corrosion-resistant and good processing performance etc., therefore Very widely used in industrial circle and daily life, application field is from automobile, electronic apparatus, machinery, aerospace field To daily necessities such as silk stocking, clothing, carpet, fishing net etc..But poor, suction that there are the impact properties under dry state and cryogenic conditions The disadvantages of aqueous larger.EVA and PA6 melt blending are prepared into EVA/PA6 alloy, the alloy can retain the good toughness of EVA, Weatherability, chemical resistance etc., and there is certain mechanical strength and wearability, so as to expand the application model of EVA material It encloses and application field.
But EVA, PA6 belong to inflammable high molecular material, the requirement with country to fire-retardant, environmentally friendly, safety etc. is got over Come it is higher, EVA/PA6 alloy material it is flame-retardant modified just become its project in the urgent need to address is widely applied.Usually it can be used Addition fire retardant to carry out EVA/PA6 alloy flame-retardant modified.
Common additive flame retardant can be divided into halogenated flame retardant and halogen-free flame retardants.
Halogenated flame retardant mainly delays or prevents the burning of polymer in gas phase.Halogenated flame retardant is liberated in the heated time-division Halogen free radical out, the free radical extract hydrogen atom from polymeric substrate, generate halogenation hydrogen molecule and gas phase is added.In gas phase In, hydrogen halides interferes hydroxyl free radical chain reaction and realizes fire-retardant fireproof and act on；On the other hand, thermal polymer degradation product occurs Variation, easily formation unsaturated hydrocarbon or even carbonization residue, so as to improve the fire retardation of condensed phase.Halogenated flame retardant There is good flame retardant effect, oneself has the history of many years as commodity, but while its is fire-retardant, also brings some serious ask Topic, is released a large amount of toxic and harmful gas (such as HC1, HBr etc.), and hydrogen halide easily absorbs the moisture in air and forms hydrogen halogen Acid has very strong corrosiveness, causes secondary public hazards；Generate a large amount of smog；Also there is serious corrosivity to process equipment. Currently, as people's awareness of environmental protection continues to increase, have become must for raw smoke and toxic gas volume when reducing fire proofing burning Right requirement.Therefore, halogenated flame retardant replaces or replaces having become fire-retardant common recognition by halogen-free flame retardants.
In halogen-free flame retardants, common inorganic hydroxide series, phosphorus flame retardant, expansion type flame retardant etc..
Common inorganic hydroxide fire-retardant agent has aluminium hydroxide, magnesium hydroxide, they have filler, fire retardant With the heavy function of smoke inhibitor 3.Its fire retardant mechanism is that metal hydroxides is thermally decomposed to generate oxide and water, this is a strong suction Thermal response can play cooling effect to polymer, and the vapor that simultaneous reactions generate can dilute fuel gas, inhibit burning Sprawling, and newborn refractory metal oxides (MgO, Al2O3) activity with higher, the hot oxygen friendship of its meeting catalytic polymer Connection reaction, heat transfer and mass transfer effect when polymer surfaces form one layer of carbonized film, and carbonized film can weaken burning, to play Fire-retardant effect.They have many advantages, such as that thermal stability is good, does not generate toxic and harmful gas, is cheap, but there are fire-retardant effects The disadvantages of rate is low, phase-splitting difference compatible with matrix resin, general fire retardant additive amount, which reaches 50 ~ 60%, just has preferable flame retardant effect, The performances such as polymer material mechanical property are influenced more.
Red phosphorus is common inorganic phosphorus fire retardant.Since its available phosphorus content is higher, in burning than other phosphorous chemical combination Object generates more phosphoric acid, therefore when reaching identical flame retardant rating, the additive amount of red phosphorus is lower than other fire retardants, but red phosphorus Major defect be itself red, it is inflammable and react production with water and have virose phosphine gas.
Expanding fire retardant is a kind of environmental protection that new development is got up, efficient flame-retarding agent.It common are expansible graphite and nitrogen-phosphorus Type expanding fire retardant.Expansible graphite is Physical expanding flame- retardant, and graphite absorbs a large amount of heat in expansion process, significantly The temperature of system is reduced, composite material in combustion, forms irregular graphite-like layer of charcoal barrier, it is gentle to reduce substrate The transmitting of heat and substance between phase, so that the substance of deep layer be prevented further to be destroyed.Expansion
Graphite has the characteristics that nontoxic, low cigarette, low burn rate and heat release rate, is a kind of environmentally friendly fire retardant.But It is that flame retarding efficiency is not also high, is seldom used alone, to be generally used in compounding with other fire retardants.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing halogen-free flameproof EVA/PA6 polymer alloy, the present invention is used Ammonium polyphosphate and the pentaerythrite composition Intumescent Retardant System with good char forming ability are added the method that melt-processed is blended Into EVA/PA6 polymer, a kind of new EVA/PA6 polymer with good flame-retardance is prepared.
The present invention to solve above-mentioned technical problem the technical solution adopted is that: it is a kind of prepare halogen-free flameproof EVA/PA6 polymerization The method of object alloy, halogen-free flameproof EVA/PA6 polymer alloy are grouped as by each group of following mass fraction: EVA50 ~ 70 Part, 10 ~ 30 parts of PA6,10 ~ 30 parts of expanding fire retardant；
The preparation method of the halogen-free flameproof EVA/PA6 polymer alloy, comprising the following steps:
1) it takes EVA50 ~ 70 part to place to be dried in vacuo in a vacuum drying oven, drying time is 12 ~ 36h, and drying temperature is 40 ~ 60 DEG C, the EVA after must drying, 10 ~ 30 parts of placements of PA6 is taken to be dried in vacuo in a vacuum drying oven, drying time is 12 ~ 36h, drying temperature are 45 ~ 80 DEG C, the PA6 after must drying；
2) it takes EVA50 ~ 70 part in step 1) after drying to be put into high-speed mixer with 10 ~ 30 parts of PA6 uniformly to mix, stir Speed is 800~1000rpm, and mixing time is 5~10min, and expanding fire retardant 10 ~ 30 is then added into high-speed mixer again Part is uniformly mixed, and mixing speed is 800~1000rpm, and mixing time is 10~15min, obtains mixed material；
3) mixed material in step 2 is put into melt blending in double screw extruder, is then granulated by extruder, obtains Halogen Fire-retardant EVA/PA6 polymer alloy.
Further, the expanding fire retardant is grouped as by each group of following mass fraction: 70 ~ 85 parts of polyphosphate, 15 ~ 30 parts of polyalcohol, the preparation method of the expanding fire retardant is the following steps are included: A, take 70 ~ 85 parts of Quadrafos, polyalcohol 15 ~ 30 parts of placements are dried in vacuo in a vacuum drying oven, and drying time is 12 ~ 36h, and drying temperature is 40 ~ 50 DEG C, obtain drying Mixture afterwards；B, mixture obtained in step A is put into high-speed mixer and is uniformly mixed, mixing speed 900 ~1000rpm, mixing time are 5~10min, obtain expanding fire retardant.
Further, the polyphosphate is ammonium polyphosphate, and the polyalcohol is monopentaerythritol or more pentaerythrites.
Further, blending temperature is 220 ~ 240 DEG C in step 3), and the blending time is 20 ~ 30min.
Further, extruder type is parallel dual-screw extruding machine in step 3).
Further, the rate of feeding of the double screw extruder is 3 ~ 6r/min, and engine speed is 150 ~ 500 r/ min。
Beneficial effects of the present invention mainly show as follows: ammonium polyphosphate (APP) is hindered using wide inorganic phosphate Fire agent, have many advantages, such as that phosphorus content height, nitrogen content height, good flame retardation effect, thermostabilization are good, press down cigarette, it is less toxic and by fire-retardant neck The highest attention in domain.But it when being used alone as fire retardant, it is larger that there is additive amounts, is improving high molecular material anti-flammability Meanwhile its other performance should be often influenced, therefore, the flame retarding efficiency for further increasing APP just becomes the concern heat of flame retardant area Point.
Ammonium polyphosphate (APP), pentaerythrite (PER) belong to the stronger substance of polarity, nylon 6(PA6) due to molecular structure In contain a large amount of amide group (- CONH-) and amino, carboxyl, so belong to highly polar high molecular material, and EVA molecule Contain a large amount of vinyl (- CH in structure2-CH2), so polarity is weaker, according to polarity " similar compatibility " theory, when PA6, When EVA, ammonium polyphosphate (APP), pentaerythrite are mixed together, APP, pentaerythrite are distributed in the stronger PA6 of polarity.? Intumescent Retardant System-ammonium polyphosphate is added in EVA/PA6 polymer and the pentaerythrite with good char forming ability forms expansion Flame-retardant system when the high polymer containing this based flame retardant is heated, can generate one layer of uniform carbonaceous foam in polymer surfaces Layer plays the role of heat-insulated, oxygen barrier, suppression cigarette, and prevents molten drop phenomenon, therefore has good anti-flammability, there is flame retarding efficiency The advantages that high and low cigarette, low toxicity, it is a kind of environmentally friendly fire retardant, meets requirement of the future society to fire retardant, be fire retardant A non-halogen developing direction, has broad application prospects.
Specific embodiment
The present invention is described in detail in conjunction with the embodiments, the present embodiment based on the technical solution of the present invention, gives Detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following embodiments.
Embodiment one
A method of prepare halogen-free flameproof EVA/PA6 polymer alloy, halogen-free flameproof EVA/PA6 polymer alloy be by with The each group of lower mass fraction is grouped as: EVA50 ~ 70 part, 10 ~ 30 parts of PA6,10 ~ 30 parts of expanding fire retardant；
The preparation method of the halogen-free flameproof EVA/PA6 polymer alloy, comprising the following steps:
1) calculate according to the mass fraction, take EVA50 ~ 70 part place be dried in vacuo in a vacuum drying oven, drying time be 12 ~ 36h, drying temperature are 40 ~ 60 DEG C, the EVA after must drying, and take 10 ~ 30 parts of PA6 to place progress vacuum in a vacuum drying oven and do Dry, drying time is 12 ~ 36h, and drying temperature is 45 ~ 80 DEG C, the PA6 after must drying；
2) it takes EVA50 ~ 70 part in step 1) after drying to be put into high-speed mixer with 10 ~ 30 parts of PA6 uniformly to mix, stir Speed is 800~1000rpm, and mixing time is 5~10min, and expanding fire retardant 10 ~ 30 is then added into high-speed mixer again Part is uniformly mixed, and mixing speed is 800~1000rpm, and mixing time is 10~15min, obtains mixed material；
3) mixed material in step 2 is put into melt blending in double screw extruder, is then granulated by extruder, obtains Halogen Fire-retardant EVA/PA6 polymer alloy.
Further, the expanding fire retardant is grouped as by each group of following mass fraction: 70 ~ 85 parts of polyphosphate, 15 ~ 30 parts of polyalcohol, the preparation method of the expanding fire retardant is the following steps are included: A, take 70 ~ 85 parts of Quadrafos, polyalcohol 15 ~ 30 parts of placements are dried in vacuo in a vacuum drying oven, and drying time is 12 ~ 36h, and drying temperature is 40 ~ 50 DEG C, obtain drying Mixture afterwards；B, mixture obtained in step A is put into high-speed mixer and is uniformly mixed, mixing speed 900 ~1000rpm, mixing time are 5~10min, obtain uniformly mixed mixed material；C, mixed material obtained in step B is put Enter melt blending in double screw extruder, blending temperature is 150 ~ 170 DEG C, and the blending time is 15 ~ 20min, then passes through extrusion Machine is granulated, and obtains expanding fire retardant；
Further, the polyphosphate is ammonium polyphosphate, and the polyalcohol is monopentaerythritol or more pentaerythrites.
Further, blending temperature is 220 ~ 240 DEG C in step 3), and the blending time is 20 ~ 30min.
Further, extruder type is parallel dual-screw extruding machine in step 3).
Further, the rate of feeding of the double screw extruder is 3 ~ 6r/min, and engine speed is 150 ~ 500 r/ min。
Embodiment two
A method of halogen-free flameproof EVA/PA6 polymer alloy being prepared, halogen-free flameproof EVA/PA6 polymer alloy is by following The each group of mass fraction is grouped as: EVA50 ~ 70 part, 10 ~ 30 parts of PA6,10 ~ 30 parts of expanding fire retardant；
The preparation method of the halogen-free flameproof EVA/PA6 polymer alloy, comprising the following steps:
1) EVA518.4g placement is taken to be dried in vacuo in a vacuum drying oven, drying time is 12 ~ 36h, drying temperature 40 ~ 60 DEG C, the EVA after must drying, take PA6 129.6g placement be dried in vacuo in a vacuum drying oven, drying time be 12 ~ 36h, drying temperature are 45 ~ 80 DEG C, the PA6 after must drying；
2) it takes EVA518.4g the and PA6 129.6g in step 1) after drying to be put into high-speed mixer uniformly to mix, stirring speed Degree is 800~1000rpm, and mixing time is 5~10min, and expanding fire retardant 252g (resistance is then added into high-speed mixer again Combustion agent accounts for the 28% of gross mass) uniformly mixed, mixing speed is 800~1000rpm, and mixing time is 10~15min, is obtained Mixed material；
3) mixed material in step 2 is put into melt blending in double screw extruder, is then granulated by extruder, obtains Halogen Fire-retardant EVA/PA6 polymer alloy.
Further, the expanding fire retardant is grouped as by each group of following mass fraction: polyphosphate 201.6g, The pentaerythrite of 50.4g, the preparation method of the expanding fire retardant is the following steps are included: A, take Quadrafos 201.6g, Ji Wusi Alcohol 50.4g placement is dried in vacuo in a vacuum drying oven, and drying time is 12 ~ 36h, and drying temperature is 40 ~ 50 DEG C, is obtained dry Mixture after dry；B, mixture obtained in step A is put into high-speed mixer and is uniformly mixed, mixing speed is 900~1000rpm, mixing time are 5~10min, obtain expanding fire retardant；
Further, the polyphosphate is ammonium polyphosphate, and the polyalcohol is monopentaerythritol or more pentaerythrites.
Further, blending temperature is 225 DEG C in step 3), and the blending time is 20 ~ 30min.
Further, extruder type is parallel dual-screw extruding machine in step 3).
Further, the rate of feeding of the double screw extruder is 3 ~ 6r/min, and engine speed is 150 ~ 500 r/ min。
Sample carries out drying and processing after the present embodiment is granulated, and then melts in plastic-injection moulding machine, in plate sulphur Pressing plate in change machine, cuts out sample, the oxygen index (OI) and vertical combustion grade of last test batten, and EVA/PA6 prepared by the embodiment is poly- The oxygen index (OI) for closing object sample is 34.3%, and vertical combustion has excellent flame retardant property up to V-0 grades of UL-94.
Embodiment three
A method of preparing halogen-free flameproof EVA/PA6 polymer alloy, comprising the following steps:
1) take EVA612g placement be dried in vacuo in a vacuum drying oven, drying time be 12 ~ 36h, drying temperature be 40 ~ 60 DEG C, the EVA after must drying, PA6 153g placement is taken to be dried in vacuo in a vacuum drying oven, drying time is 12 ~ 36h, Drying temperature is 45 ~ 80 DEG C, the PA6 after must drying；
2) it takes EVA612g the and PA6 153g in step 1) after drying to be put into high-speed mixer uniformly to mix, mixing speed is 800~1000rpm, mixing time are 5~10min, and expanding fire retardant 135g(fire retardant is then added into high-speed mixer again Account for the 15% of gross mass) uniformly mixed, mixing speed is 800~1000rpm, and mixing time is 10~15min, must be mixed Material；
3) mixed material in step 2 is put into melt blending in double screw extruder, is then granulated by extruder, obtains Halogen Fire-retardant EVA/PA6 polymer alloy.
Further, the expanding fire retardant is grouped as by each group of following mass fraction: ammonium polyphosphate 108g, 27g Pentaerythrite, the preparation method of the expanding fire retardant is the following steps are included: A, take Quadrafos 108g, pentaerythrite 27g to place It is dried in vacuo in a vacuum drying oven, drying time is 12 ~ 36h, and drying temperature is 40 ~ 50 DEG C, the mixing after must drying Object；B, mixture obtained in step A is put into high-speed mixer and is uniformly mixed, mixing speed be 900~ 1000rpm, mixing time are 5~10min, obtain expanding fire retardant；
Further, blending temperature is 225 DEG C in step 3), and the blending time is 20 ~ 30min.
Further, extruder type is parallel dual-screw extruding machine in step 3).
Further, the rate of feeding of the double screw extruder is 3 ~ 6r/min, and engine speed is 150 ~ 500 r/ min。
Sample carries out drying and processing after the present embodiment is granulated, and then melts in plastic-injection moulding machine, in plate sulphur Pressing plate in change machine cuts out sample, and the oxygen index (OI) and vertical combustion grade of last test batten, prepared EVA/PA6 is poly- under this condition The oxygen index (OI) for closing object alloy batten is 24.3%, and for vertical combustion up to V-2 grades of UL-94, flame retardant property is general.
Comparative example: a method of preparing halogen-free flameproof EVA/PA6 polymer alloy, comprising the following steps:
1) take EVA720g placement be dried in vacuo in a vacuum drying oven, drying time be 12 ~ 36h, drying temperature be 40 ~ 60 DEG C, the EVA after must drying, PA6 180g placement is taken to be dried in vacuo in a vacuum drying oven, drying time is 12 ~ 36h, Drying temperature is 45 ~ 80 DEG C, the PA6 after must drying；
2) it takes EVA720g the and PA6 180g in step 1) after drying to be put into high-speed mixer uniformly to mix, mixing speed is 800~1000rpm, mixing time be 5~10min, then proceed in high-speed mixer with mixing speed be 800~ 1000rpm, mixing time are 10~15min, obtain mixed material；
3) mixed material in step 2 is put into melt blending in double screw extruder, is then granulated by extruder, obtains EVA/ PA6 polymer alloy.
Further, blending temperature is 225 DEG C in step 3), and the blending time is 20 ~ 30min.
Further, extruder type is parallel dual-screw extruding machine in step 3).
Further, the rate of feeding of the double screw extruder is 3 ~ 6r/min, and engine speed is 150 ~ 500 r/ min。
Sample carries out drying and processing after the present embodiment is granulated, and then melts in plastic-injection moulding machine, in plate sulphur Pressing plate in change machine cuts out sample, and the oxygen index (OI) and vertical combustion grade of last test batten, prepared EVA/PA6 is poly- under this condition The oxygen index (OI) for closing object alloy batten is 20.9%, and vertical combustion can't pass (i.e. nonrated), illustrate without flame-retardant modified EVA/PA6 polymer alloy flame retardant property is very poor.
By the fire-retardant of different quality containing is added in embodiment two, embodiment three and comparative example in EVA/PA6 polymer Influence of the agent to sample oxygen index (OI), vertical combustion grade is shown in Table 1:
Table 1
By data in table 1 it is found that by content be 28% expanding fire retardant it is modified, the anti-flammability of EVA/PA6 polymer alloy It can significantly be promoted, combustion rating is increased to V-0 grades, and oxygen refers to by can't pass of fire retardant, the V-2 of fire retardant 15% grade is not added Number obviously becomes larger.These show that the EVA/PA6 polymer alloy that expandable flame retardant agent content is 28% has excellent flame retardant property.
Test result explanation: according to national standard GBT 2406.2-2009, the oxygen index (OI) of polymer material is bigger, illustrates material More difficult to burn；According to GBT 2408-2008, the Fire retardant grade of polymer material, it is descending successively are as follows: V-0 > V-1 > V-2, V- 0 is least easy firing grade, can't pass and shows that material does not have anti-flammability or inflammable.
It should also be noted that, herein, the relational terms such as I, II, III are used merely to an entity or behaviour Make with another entity or operate distinguish, without necessarily requiring or implying between these entities or operation there are it is any this The actual relationship of kind or sequence.Moreover, the terms "include", "comprise" or its any other variant are intended to nonexcludability Include so that include a series of elements process, method, article or equipment not only include those elements, but also Including other elements that are not explicitly listed, or further include for this process, method, article or equipment intrinsic want Element.In the absence of more restrictions, the element limited by sentence "including a ...", it is not excluded that including described want There is also other identical elements in the process, method, article or equipment of element.
Each embodiment in this specification is described in a progressive manner, the highlights of each of the examples are with other The difference of embodiment, the same or similar parts in each embodiment may refer to each other.

Claims (6)

1. a kind of method for preparing halogen-free flameproof EVA/PA6 polymer alloy, it is characterised in that: halogen-free flameproof EVA/PA6 is poly- It closes object alloy to be grouped as by each group of following mass fraction: EVA50 ~ 70 part, 10 ~ 30 parts of PA6,10 ~ 30 parts of expanding fire retardant；
The preparation method of the halogen-free flameproof EVA/PA6 polymer alloy, comprising the following steps:
1) 50 ~ 70 parts of placements of EVA are taken to be dried in vacuo in a vacuum drying oven, drying time is 12 ~ 36h, and drying temperature is 40 ~ 60 DEG C, the EVA after must drying, 10 ~ 30 parts of placements of PA6 is taken to be dried in vacuo in a vacuum drying oven, drying time is 12 ~ 36h, drying temperature are 45 ~ 80 DEG C, the PA6 after must drying；
2) it takes 50 ~ 70 parts and 10 ~ 30 parts of PA6 of EVA in step 1) after drying to be put into high-speed mixer uniformly to mix, stir Speed is 800~1000rpm, and mixing time is 5~10min, and expanding fire retardant 10 ~ 30 is then added into high-speed mixer again Part is uniformly mixed, and mixing speed is 800~1000rpm, and mixing time is 10~15min, obtains mixed material；
3) mixed material in step 2 is put into melt blending in double screw extruder, is then granulated by extruder, obtains Halogen Fire-retardant EVA/PA6 polymer alloy.
2. a kind of method for preparing halogen-free flameproof EVA/PA6 polymer alloy according to claim 1, it is characterised in that: The expanding fire retardant is grouped as by each group of following mass fraction: 70 ~ 85 parts of polyphosphate, 15 ~ 30 parts of polyalcohol, this is swollen The preparation method of swollen fire retardant is the following steps are included: A, take that 70 ~ 85 parts of Quadrafos, 15 ~ 30 parts of polyalcohol to be placed on vacuum dry It is dried in vacuo in dry case, drying time is 12 ~ 36h, and drying temperature is 40 ~ 50 DEG C, the mixture after must drying；It B, will step Mixture obtained in rapid A, which is put into high-speed mixer, uniformly to be mixed, and mixing speed is 900~1000rpm, mixing time For 5~10min, expanding fire retardant is obtained.
3. a kind of method for preparing halogen-free flameproof EVA/PA6 polymer alloy according to claim 2, it is characterised in that: The polyphosphate is ammonium polyphosphate, and the polyalcohol is monopentaerythritol or more pentaerythrites.
4. a kind of method for preparing halogen-free flameproof EVA/PA6 polymer alloy according to claim 1, it is characterised in that: Blending temperature is 220 ~ 240 DEG C in step 3), and the blending time is 20 ~ 30min.
5. a kind of method for preparing halogen-free flameproof EVA/PA6 polymer alloy according to claim 1, it is characterised in that: Extruder type is parallel dual-screw extruding machine in step 3).
6. a kind of method for preparing halogen-free flameproof EVA/PA6 polymer alloy according to claim 1, it is characterised in that: The rate of feeding of the double screw extruder is 3 ~ 6r/min, and engine speed is 150 ~ 500 r/min.
CN201811073522.9A 2018-09-14 2018-09-14 A method of preparing halogen-free flameproof EVA/PA6 polymer alloy Pending CN109337185A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811073522.9A CN109337185A (en) 2018-09-14 2018-09-14 A method of preparing halogen-free flameproof EVA/PA6 polymer alloy

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811073522.9A CN109337185A (en) 2018-09-14 2018-09-14 A method of preparing halogen-free flameproof EVA/PA6 polymer alloy

Publications (1)

Publication Number Publication Date
CN109337185A true CN109337185A (en) 2019-02-15

Family

ID=65305169

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811073522.9A Pending CN109337185A (en) 2018-09-14 2018-09-14 A method of preparing halogen-free flameproof EVA/PA6 polymer alloy

Country Status (1)

Country Link
CN (1) CN109337185A (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101125954A (en) * 2006-08-14 2008-02-20 刘士祥 Formulation for alloy coagulated nylon
CN101205324A (en) * 2007-12-11 2008-06-25 杭州捷尔思阻燃化工有限公司 Halogen-free flame-retardant electric wire and cable sheath polymer material and uses thereof
CN103881221A (en) * 2013-06-25 2014-06-25 浙江奥强环保科技有限公司 Flame-retardant and antistatic nylon composite material and preparation method thereof
CN103923376A (en) * 2014-04-24 2014-07-16 上海交通大学 Dynamic vulcanized inflaming retarding nylon/ethylene vinyl acetate rubber thermoplastic elastomer and preparation method thereof
CN105462245A (en) * 2015-12-30 2016-04-06 广东国立科技股份有限公司 Ultralow-temperature-resistant glass-fiber-reinforced PA6/EVA (polyamide 6/ethylene-vinyl acetate) alloy material and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101125954A (en) * 2006-08-14 2008-02-20 刘士祥 Formulation for alloy coagulated nylon
CN101205324A (en) * 2007-12-11 2008-06-25 杭州捷尔思阻燃化工有限公司 Halogen-free flame-retardant electric wire and cable sheath polymer material and uses thereof
CN103881221A (en) * 2013-06-25 2014-06-25 浙江奥强环保科技有限公司 Flame-retardant and antistatic nylon composite material and preparation method thereof
CN103923376A (en) * 2014-04-24 2014-07-16 上海交通大学 Dynamic vulcanized inflaming retarding nylon/ethylene vinyl acetate rubber thermoplastic elastomer and preparation method thereof
CN105462245A (en) * 2015-12-30 2016-04-06 广东国立科技股份有限公司 Ultralow-temperature-resistant glass-fiber-reinforced PA6/EVA (polyamide 6/ethylene-vinyl acetate) alloy material and preparation method thereof

Similar Documents

Publication Publication Date Title
CN101845197B (en) High-performance halogen-free flame retardant ABS modified resin and preparation method thereof
CN101293983B (en) Expansion flame-proof polypropelene composition and preparation method thereof
CN112250935B (en) High-flame-retardant-grade low-smoke halogen-free material and preparation method and application thereof
CN101875745B (en) Flame-retardant styrene polymer compound containing smoke inhibitor and preparation method thereof
CN101402758B (en) Non-halogen flame-proof polyvinyl composite and method of producing the same
CN101735514B (en) Flame-retardant polypropylene material and preparation method
CN103289290B (en) A kind of phosphorus system synergistic flame-retardant ABS compound material and preparation method thereof
CN101857712B (en) Halogen-free flame-retardant ABS/PET alloy and preparation method thereof
CN104530626A (en) Halogen-free flame retardant thermoplastic elastomer cable material and preparation method thereof
CN103131084B (en) A kind of halogen-free flameproof permanent anti-static PP composite material and preparation method
CN101831109B (en) Halogen-free expanded flame-retardant polypropylene film
CN111333960A (en) Antimony-free flame-retardant polypropylene composition and preparation method thereof
CN101659778A (en) Expanded halogen-free flame-retardant ABS compound material
CN109280259B (en) EVA/PA6 flame-retardant composite material added with OMMT in distribution regulation and control mode and preparation method
CN102101941A (en) Flame-retarding polyphenyl ether composite, and preparation method and use thereof
CN104693599A (en) Method for preparing halogen-free flame retardant polypropylene modified material
CN113248813B (en) Efficient halogen-free flame-retardant cable material and preparation method thereof
CN106700227A (en) Polypropylene nanometer montmorillonite intumescent flame-retardant composite and preparation method thereof
CN108034126B (en) Halogen-free flame-retardant polyolefin composite material and preparation method thereof
CN102936402A (en) Low-smoke heat-resistant halogen-free flame-retardant polycarbonate/acrylonitrile-butadiene-styrene resin composition and preparation method thereof
CN107868460A (en) A kind of halogen-free flame-retardant resin and preparation method thereof
CN102061072A (en) Environment-friendly halogen-free non-phosphorus flame-retardant polycarbonate resin composition
CN115505172B (en) Halogen-free flame retardant, and preparation method and application thereof
CN109337185A (en) A method of preparing halogen-free flameproof EVA/PA6 polymer alloy
CN103396640B (en) A kind of super soft halogen-free flame-retardant thermoplastic elastomer and preparation method thereof

Legal Events

Date Code Title Description
PB01 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: 20190215