CN110467777A - A kind of low linear expansion coefficient halogen-free anti-flaming polypropylene material and preparation method thereof - Google Patents
A kind of low linear expansion coefficient halogen-free anti-flaming polypropylene material and preparation method thereof Download PDFInfo
- Publication number
- CN110467777A CN110467777A CN201910806426.9A CN201910806426A CN110467777A CN 110467777 A CN110467777 A CN 110467777A CN 201910806426 A CN201910806426 A CN 201910806426A CN 110467777 A CN110467777 A CN 110467777A
- Authority
- CN
- China
- Prior art keywords
- halogen
- temperature
- expansion coefficient
- linear expansion
- area
- 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
- 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
-
- 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)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of low-expansion coefficient halogen-free polypropylene flame redardants and preparation method thereof, which is made of the raw material of following parts by weight: 52~72 parts of polypropylene；3~8 parts of compatilizer；20~25 parts of halogen-free flame retardants；5~15 parts of eucryptite premix；0.1-0.3 parts of promotor；0.2 part of primary antioxidant, 0.2 part of auxiliary anti-oxidant, 0.5 part of lubricant；A kind of preparation method of low-expansion coefficient halogen-free polypropylene flame redardant is also disclosed simultaneously.Halogen-free anti-flaming polypropylene material of the invention has the characteristics that there is low linear expansion coefficient, excellent flame retardant property.
Description
Technical field
The present invention relates to a kind of low linear expansion coefficient halogen-free anti-flaming polypropylene materials and preparation method thereof, belong to macromolecule
Field of material technology.
Background technique
Polypropylene (PP) raw material have cheap, light weight, solvent resistant, Yi Huishou, nontoxic, comprehensive mechanical property is good
The features such as, so that it is widely used in the fields such as household electrical appliances, automobile, electronic apparatus.However, oxygen refers to since its carbon-chain structure is inflammable
Number is lower, thus is restricted in some charging members, thus many applications require it is carried out it is flame-retardant modified.Mesh
It is preceding that flame-retardant modified method predominantly addition fire retardant is carried out to polypropylene both at home and abroad.There are mainly of two types at present for fire retardant,
I.e. traditional halogen containing flame-retardant (halogen-antimony composite flame retardant system) and novel halogen-free flame retardants.Halogen containing flame-retardant is due to smoke amount
Greatly, the hydrogen halide released has corrosivity, generates secondary pollution to environment, therefore, substitutes bromine antimony using halogen-free flameproof
The fire-retardant development trend as industry.Expansion type flame retardant is phosphorous nitrogen compound mostly, mainly by forming porous foam
Layer of charcoal plays fire retardation in condensed phase, thus smoke amount is low, to more environment-friendly.
Simultaneously, polypropylene linear expansion coefficient is higher (9.05 × 10-5/K), causes it in the application in certain fields
Limit value is received, there is different degrees of contraction because of the variation of ambient temperature, it is caused short slab occur in application aspect in product,
Such as product size is unstable, abnormal sound.Currently, mainly by the way that the methods of glass fibre, wollastonite, talcum powder is added come significantly
The linear expansion coefficient and shrinking percentage of material are reduced, but glass fibre modified polypropene will lead to product and be easy warpage, and talcum
Powder modified polypropene reduces the shrinking percentage of material and linear expansion coefficient effect is not it is obvious that and can reduce halogen-free flameproof PP resistance
Combustion property.Also having through elastomer, whisker reduces material shrinkage and linear expansion coefficient, but elasticity of import body and whisker
Cost is very high, and can reduce halogen-free polypropylene flame redardant anti-flammability, can not accomplish that low linear expansion coefficient is taken into account with halogen-free flameproof.
CN102504411A discloses a kind of low linear-expansion-coefficient polypropylene composite and preparation method thereof, including poly- third
Alkene 95-53%, heat stabilizer 0-1%, lubricant 0-1%, toughener 0-20%, interfacial compatibilizer 0-5%, wollastonite 5-
20%, wherein the wollastonite is that acicular wollastonite of the draw ratio between 10-30 and the powdery wollastonite of draw ratio≤5 press 1/
The mixture of the ratio mixing of 4-4.The main method combined by acicular wollastonite with powdery wollastonite obtains a kind of low linear
Coefficient of expansion polypropylene composite, horizontal and vertical linear expansion coefficient reach 4.0 × 10-5 or less.
CN103665544A discloses a kind of Isotropic polypropylene composition with low linear expansion coefficient and preparation method thereof,
The polypropene composition can make the horizontal and vertical linear expansion coefficient of polypropene composition reach by the addition of whisker
To 4.0 × 10-5 hereinafter, and reaching isotropic purpose.
CN106317607A discloses a kind of ultralow linear expansion coefficient PP composite material and preparation method thereof, passes through
One-dimensional Sc2W3O12 is added, ultralow linear expansion coefficient composite material is prepared.
The present invention uses the halogen-free flame retardants of piperazine pyrophosphate system, compounds beta-eucryptite, is aided with efficient compatilizer, promotion
Agent overcomes polypropylene disadvantages described above, and the low linear expansion coefficient of excellent in mechanical performance, the nothing of excellent fire-retardancy is prepared
Halogen anti-flaming polypropylene material.
Summary of the invention
The present invention be directed to the shortcomings of the prior art, the present invention uses the halogen-free flame retardants of piperazine pyrophosphate system,
Beta-eucryptite is compounded, efficient compatilizer and promotor are aided with, the low linear expansion coefficient halogen-free flameproof poly- third haveing excellent performance is made
Alkene material is mainly used for household electrical appliances application field, meets actual operation requirements.
To solve the above problems, the technical solution used in the present invention is as follows:
A kind of low linear expansion coefficient halogen-free flame-retardant polypropylene composition, is prepared by the raw material of following parts by weight:
The eucryptite premix is the premix of beta-eucryptite and titanate esters inorganic agent.
As an improvement of the above technical solution, the acrylic resin is copolymer polypropylene, melt index 2-15g/
10min, testing standard are GB/T 3682-2000, and test temperature is 230 DEG C, are loaded as 2.16kg.
As an improvement of the above technical solution, the compatilizer is maleic anhydride grafted ethene octene copolymer.
As an improvement of the above technical solution, the halogen-free flame retardants is piperazine pyrophosphate system fire retardant.
As an improvement of the above technical solution, the promotor is triallyl cyanurate, triallyl isocyanide urea
At least one of acid esters is several.
As an improvement of the above technical solution, the primary antioxidant is Hinered phenols antioxidant, and auxiliary anti-oxidant is phosphorous
Acid esters kind antioxidant, lubricant are the sour glycerine ester of single 18 (alkane).
Specifically, the preparation method of the low linear expansion coefficient halogen-free anti-flaming polypropylene material includes the following steps:
(1) eucryptite drying 3~5 hours at 100~120 DEG C are placed in baking oven to use beta-eucryptite after cooling
100 DEG C of 2% titanate coupling agent, temperature, 1000~1500 revs/min of mixed at high speed of revolving speed handle 5min, β-lithium are prepared
Nepheline premix；
(2) raw material is weighed by weight ratio；
(3) by weighed each raw material mixed at high speed 2min, 80 DEG C of temperature, 1000 revs/min of revolving speed, after mixing plus
To double screw extruder, processing technology are as follows: 180~200 DEG C of area's temperature, two 180~200 DEG C of area's temperature, three area's temperature 180~
200 DEG C, four 180~200 DEG C of area's temperature, five 170~180 DEG C of area's temperature, 180~200 DEG C of head temperature, engine speed 400~
500 revs/min；
(4) water cooling, drying, pelletizing are after squeezing out to get low linear expansion coefficient halogen-free anti-flaming polypropylene material.
As an improvement of the above technical solution, the screw configuration of the double screw extruder is single thread；Spiro rod length L
It is 35~60 with the ratio between diameter D L/D；The screw rod is equipped with 1 or more gear block area and 1 or more left-hand thread area.
As an improvement of the above technical solution, the ratio between described spiro rod length L and diameter D L/D is 40~50；On the screw rod
Equipped with 3 gear block areas and 1 left-hand thread area.
The principle of the present invention is as follows: eucryptite is a kind of lithium aluminosilicate mineral, and molecular formula is " LiAl-Si04 or Li2O
A12032Si02 is in round and smooth lumps or star spot shape more；Due to the unique architectural characteristic of beta-eucryptite, make beta-eucryptite at
For one of the exotic materials with negative thermal expansion coefficient a small number of in nature (coefficient of expansion -6.2*10-6/K).According to the heat of material
The coefficient of expansion has the characteristic of additive property, and people are usually compound with other materials by beta-eucryptite, prepare with low bulk or
The composite material of " zero thermal expansion ".The present invention is based on the negative dilatancy characteristic of beta-eucryptite, the high expansions of modified polypropylene material
Characteristic obtains the PP composite material of low expansion coefficient.It is first in order to make full use of the negative dilatancy characteristic of beta-eucryptite
The dispersibility that first solve the problems, such as beta-eucryptite makes beta-eucryptite and polypropylene material form unified entirety, to β-lithium rosy clouds
Stone, which pre-processes and adds efficient compatilizer, has well solved this problem.
Meanwhile the nitrogen phosphorus Intumescent Retardant System that the present invention uses, mainly in condensed phase and forming porous foam layer of charcoal
Fire retardation is played, addition common inorganic packing material has very havoc at carbon to halogen-free flame-retardant system, so as to cause fire-retardant
Performance decline.The present invention passes through preferred piperazine pyrophosphate system halogen-free flame retardants, under the catalysis of promotor, beta-eucryptite and nothing
Halogen fire retardant forms positive synergistic effect, beta-eucryptite and halogen-free flame retardants, and (aerobic or anaerobic has flame or nothing under high temperature action
Flame), chemical reaction is generated, hard ceramic compound is produced, there is thermal insulation, oxygen-impermeable effect, it is fire-retardant to material that there is promotion
Effect
Compared with prior art, implementation result of the invention is as follows by the present invention:
Halogen-free anti-flaming polypropylene material of the invention has the characteristics that low linear expansion coefficient, excellent flame retardant property.
Detailed description of the invention
Fig. 1 is the preparation technology flow chart of low linear expansion coefficient halogen-free polypropylene flame redardant of the present invention；
Fig. 2 is the reaction mechanism figure that titanate esters of the present invention pre-process beta-eucryptite.
Specific embodiment
Illustrate the contents of the present invention below in conjunction with specific embodiments.
To further understand the features of the present invention, technological means and specific purposes achieved, function, parse this hair
The advantages of with spirit, by following embodiment, the present invention is further elaborated.
Titanate coupling agent by it alkoxy directly and the adsorbed micro carboxyl in beta-eucryptite surface or hydroxyl into
Row chemical action and be coupled, improve beta-eucryptite and polypropylene matrix resin compatibility.
The reaction mechanism of titanate esters pretreatment beta-eucryptite of the present invention, as shown in Figure 2.
Raw material used in the embodiment of the present invention is as follows:
Polypropylene (PP) resin: MN10-S is copolymerized PP, melt index 10g/10min, middle petrochemical industry Maoming company；
Compatilizer: PC-28, maleic anhydride grafted ethene-octene copolymer (POE-g-MAH), maleic anhydride grafting ratio
0.8%-1.2%, Guangdong Bai Chen chemical industry；
Halogen-free flame retardants: FP2200, piperazine pyrophosphate system halogen-free flame retardants, Japanese ADK company；
Beta-eucryptite: technical grade, 2000 mesh, Chen Dong new material Co., Ltd；
Primary antioxidant: four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters (antioxidant 1010), it is auspicious
Scholar Ciba；
Auxiliary antioxidant: phosphorous acid three (2,4- di-tert-butyl-phenyl) ester (irgasfos 168), Ciba, Switzerland；
Lubricant: amides Lubricate EBS B50, Sichuan sky chemistry；
Titanate coupling agent: NDZ-201, isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, Nanjing dawn chemical industry
Group.
Embodiment 1:
Low linear expansion coefficient halogen-free flame-retardant polypropylene composition described in this comparative example, is prepared from the following raw materials:
The preparation method of above-mentioned low linear expansion coefficient halogen-free anti-flaming polypropylene material, comprising the following steps:
(1) eucryptite is placed in 120 DEG C drying 3 hours in baking oven, after cooling, by eucryptite 2% titanate esters idol
Join agent, 100 DEG C of temperature, 1000 revs/min of mixed at high speed of revolving speed handle 5min, beta-eucryptite premix is prepared；
(2) beta-eucryptite premix that step (1) mixes and other weighed each raw materials are added to mixed at high speed
In machine, mixed at high speed 2min, 80 DEG C of temperature, 1000 revs/min of revolving speed；
(3) mixture that step (2) mixes is added twin-screw extrude through feeder, processing technology are as follows: an area
180 DEG C of temperature, two 180 DEG C of area's temperature, three 180 DEG C of area's temperature, four 180 DEG C of area's temperature, five 170 DEG C of area's temperature, head temperature 200
DEG C, 400 revs/min of engine speed.
Note: the ratio between spiro rod length L and diameter D L/D are 40, and screw rod is equipped with 2 gear block areas and 1 left-hand thread area.
Embodiment 2:
Low linear expansion coefficient halogen-free flame-retardant polypropylene composition described in this comparative example, is prepared from the following raw materials:
The preparation method of above-mentioned low linear expansion coefficient halogen-free anti-flaming polypropylene material the following steps are included:
(1) eucryptite is placed in 100 DEG C drying 4 hours in baking oven, after cooling, by eucryptite 2% titanate esters idol
Join agent, 100 DEG C of temperature, 1500 revs/min of mixed at high speed of revolving speed handle 5min, beta-eucryptite premix is prepared；
(2) beta-eucryptite premix that step (1) mixes and other weighed each raw materials are added to mixed at high speed
In machine, mixed at high speed 2min, 80 DEG C of temperature, 1000 revs/min of revolving speed；
(3) mixture that step (2) mixes is added twin-screw extrude through feeder, processing technology are as follows: an area
190 DEG C of temperature, two 190 DEG C of area's temperature, three 190 DEG C of area's temperature, four 190 DEG C of area's temperature, five 180 DEG C of area's temperature, head temperature 190
DEG C, 450 revs/min of engine speed.
Note: the ratio between spiro rod length L and diameter D L/D are 40, and screw rod is equipped with 2 gear block areas and 1 left-hand thread area.
Embodiment 3:
Low linear expansion coefficient halogen-free flame-retardant polypropylene composition described in this comparative example, is prepared from the following raw materials:
The preparation method of above-mentioned low linear expansion coefficient halogen-free anti-flaming polypropylene material the following steps are included:
(1) eucryptite is set in baking oven and is dried 5 hours at 100 DEG C, after cooling, by 2% titanate esters of eucryptite
100 DEG C of coupling agent, temperature, 1200 revs/min of mixed at high speed of revolving speed handle 5min, beta-eucryptite premix are prepared；
(2) beta-eucryptite premix that step (1) mixes and other weighed each raw materials are added to mixed at high speed
In machine, mixed at high speed 2min, 80 DEG C of temperature, 1000 revs/min of revolving speed；
(3) mixture that step (2) mixes is added twin-screw extrude through feeder, processing technology are as follows: an area
190 DEG C of temperature, two 190 DEG C of area's temperature, three 190 DEG C of area's temperature, four 190 DEG C of area's temperature, five 180 DEG C of area's temperature, head temperature 200
DEG C, 450 revs/min of engine speed.
Note: the ratio between spiro rod length L and diameter D L/D are 40, and screw rod is equipped with 2 gear block areas and 1 left-hand thread area.
Embodiment 4:
Low linear expansion coefficient halogen-free flame-retardant polypropylene composition described in this comparative example, is prepared from the following raw materials:
The preparation method of above-mentioned low linear expansion coefficient halogen-free anti-flaming polypropylene material the following steps are included:
(1) eucryptite is placed in 120 DEG C drying 4 hours in baking oven, after cooling, by eucryptite 2% titanate esters idol
Join agent, 100 DEG C of temperature, 1500 revs/min of mixed at high speed of revolving speed handle 5min, beta-eucryptite premix is prepared；
(2) beta-eucryptite premix that step (1) mixes and other weighed each raw materials are added to mixed at high speed
In machine, mixed at high speed 2min, 80 DEG C of temperature, 1000 revs/min of revolving speed；
(3) mixture that step (2) mixes is added twin-screw extrude through feeder, processing technology are as follows: an area
200 DEG C of temperature, two 200 DEG C of area's temperature, three 200 DEG C of area's temperature, four 200 DEG C of area's temperature, five 180 DEG C of area's temperature, head temperature 200
DEG C, 450 revs/min of engine speed.
Note: the ratio between spiro rod length L and diameter D L/D are 40, and screw rod is equipped with 2 gear block areas and 1 left-hand thread area.
Embodiment 5:
Low linear expansion coefficient halogen-free flame-retardant polypropylene composition described in this comparative example, is prepared from the following raw materials:
The preparation method of above-mentioned low linear expansion coefficient halogen-free anti-flaming polypropylene material the following steps are included:
(1) eucryptite is placed in 120 DEG C drying 4 hours in baking oven, after cooling, by eucryptite 2% titanate esters idol
Join agent, 100 DEG C of temperature, 1500 revs/min of mixed at high speed of revolving speed handle 5min, beta-eucryptite premix is prepared；
(2) beta-eucryptite premix that step (1) mixes and other weighed each raw materials are added to mixed at high speed
In machine, mixed at high speed 2min, 80 DEG C of temperature, 1000 revs/min of revolving speed；
(3) mixture that step (2) mixes is added twin-screw extrude through feeder, processing technology are as follows: an area
200 DEG C of temperature, two 200 DEG C of area's temperature, three 200 DEG C of area's temperature, four 200 DEG C of area's temperature, five 180 DEG C of area's temperature, head temperature 200
DEG C, 450 revs/min of engine speed.
Note: the ratio between spiro rod length L and diameter D L/D are 45, and screw rod is equipped with 2 gear block areas and 1 left-hand thread area.
Embodiment 6:
Low linear expansion coefficient halogen-free flame-retardant polypropylene composition described in this comparative example, is prepared from the following raw materials:
The preparation method of above-mentioned low linear expansion coefficient halogen-free anti-flaming polypropylene material the following steps are included:
(1) eucryptite is placed in 120 DEG C drying 4 hours in baking oven, after cooling, by eucryptite 2% titanate esters idol
Join agent, 100 DEG C of temperature, 1500 revs/min of mixed at high speed of revolving speed handle 5min, beta-eucryptite premix is prepared；
(2) beta-eucryptite premix that step (1) mixes and other weighed each raw materials are added to mixed at high speed
In machine, mixed at high speed 2min, 80 DEG C of temperature, 1000 revs/min of revolving speed；
(3) mixture that step (2) mixes is added twin-screw extrude through feeder, processing technology are as follows: an area
200 DEG C of temperature, two 200 DEG C of area's temperature, three 200 DEG C of area's temperature, four 200 DEG C of area's temperature, five 180 DEG C of area's temperature, head temperature 200
DEG C, 450 revs/min of engine speed.
Note: the ratio between spiro rod length L and diameter D L/D are 45, and screw rod is equipped with 2 gear block areas and 1 left-hand thread area.
Embodiment 7:
Low linear expansion coefficient halogen-free flame-retardant polypropylene composition described in this comparative example, is prepared from the following raw materials:
The preparation method of above-mentioned low linear expansion coefficient halogen-free anti-flaming polypropylene material the following steps are included:
(1) eucryptite is placed in 120 DEG C drying 4 hours in baking oven, after cooling, by eucryptite 2% titanate esters idol
Join agent, 100 DEG C of temperature, 1500 revs/min of mixed at high speed of revolving speed handle 5min, beta-eucryptite premix is prepared；
(2) beta-eucryptite premix that step (1) mixes and other weighed each raw materials are added to mixed at high speed
In machine, mixed at high speed 2min, 80 DEG C of temperature, 1000 revs/min of revolving speed；
(3) mixture that step (2) mixes is added twin-screw extrude through feeder, processing technology are as follows: an area
200 DEG C of temperature, two 200 DEG C of area's temperature, three 200 DEG C of area's temperature, four 200 DEG C of area's temperature, five 180 DEG C of area's temperature, head temperature 200
DEG C, 450 revs/min of engine speed.
Note: the ratio between spiro rod length L and diameter D L/D are 50, and screw rod is equipped with 3 gear block areas and 1 left-hand thread area.
Comparative example 1:
Low linear expansion coefficient halogen-free flame-retardant polypropylene composition described in this comparative example, is prepared from the following raw materials:
The preparation method of above-mentioned low linear expansion coefficient halogen-free anti-flaming polypropylene material the following steps are included:
(1) weighed each raw material is added in high-speed mixer, mixed at high speed 2min (80 DEG C of temperature, revolving speed 1000
Rev/min)；
(2) mixture that step (1) mixes is added twin-screw extrude through feeder, processing technology are as follows: an area
200 DEG C of temperature, two 200 DEG C of area's temperature, three 200 DEG C of area's temperature, four 200 DEG C of area's temperature, five 180 DEG C of area's temperature, head temperature 200
DEG C, 450 revs/min of engine speed.
Wherein, the ratio between spiro rod length L and diameter D L/D are 50, and screw rod is equipped with 3 gear block areas and 1 left-hand thread area.
Comparative example 2:
Low linear expansion coefficient halogen-free flame-retardant polypropylene composition described in this comparative example, is prepared from the following raw materials:
The preparation method of above-mentioned low linear expansion coefficient halogen-free anti-flaming polypropylene material, comprising the following steps:
(1) wollastonite is placed in 120 DEG C drying 4 hours in baking oven, after cooling, by wollastonite 2% titanate esters idol
Join agent, 100 DEG C of temperature, 1500 revs/min of mixed at high speed of revolving speed handle 5min, wollastonite premix is prepared；
(2) wollastonite that step (1) mixes and other weighed each raw materials are added in high-speed mixer, high speed
Mix 2min, 80 DEG C of temperature, 1000 revs/min of revolving speed；
(3) mixture that step (2) mixes is added twin-screw extrude through feeder, processing technology are as follows: an area
200 DEG C of temperature, two 200 DEG C of area's temperature, three 200 DEG C of area's temperature, four 200 DEG C of area's temperature, five 180 DEG C of area's temperature, head temperature 200
DEG C, 450 revs/min of engine speed.
Wherein, the ratio between spiro rod length L and diameter D L/D are 50, and screw rod is equipped with 3 gear block areas and 1 left-hand thread area.
Comparative example 3:
Low linear expansion coefficient halogen-free flame-retardant polypropylene composition described in this comparative example, is prepared from the following raw materials:
The preparation method of above-mentioned low linear expansion coefficient halogen-free anti-flaming polypropylene material the following steps are included:
(1) talcum powder is placed in 120 DEG C drying 4 hours in baking oven, after cooling, by talcum powder 2% titanate esters idol
Join agent, 100 DEG C of temperature, 1500 revs/min of mixed at high speed of revolving speed handle 5min, talcum powder premix is prepared；
(2) talcum powder that step (1) mixes and other weighed each raw materials are added in high-speed mixer, high speed
Mix 2min, 80 DEG C of temperature, 1000 revs/min of revolving speed；
(3) mixture that step (2) mixes is added twin-screw extrude through feeder, processing technology are as follows: an area
200 DEG C of temperature, two 200 DEG C of area's temperature, three 200 DEG C of area's temperature, four 200 DEG C of area's temperature, five 180 DEG C of area's temperature, head temperature 200
DEG C, 450 revs/min of engine speed.
Wherein, the ratio between spiro rod length L and diameter D L/D are 50, and screw rod is equipped with 3 gear block areas and 1 left-hand thread area.
Comparative example 4:
Low linear expansion coefficient halogen-free flame-retardant polypropylene composition described in this comparative example, is prepared from the following raw materials:
The preparation method of above-mentioned low linear expansion coefficient halogen-free anti-flaming polypropylene material, comprising the following steps:
(1) whisker is placed in 120 DEG C drying 4 hours in baking oven, after cooling, by 2% titanate coupling agent of whisker,
100 DEG C of temperature, 1500 revs/min of mixed at high speed of revolving speed handle 5min, and whisker premix is prepared；
(2) whisker that step (1) mixes and other weighed each raw materials are added in high-speed mixer, high speed is mixed
Close 2min, 80 DEG C of temperature, 1000 revs/min of revolving speed；
(3) mixture that step (2) mixes is added twin-screw extrude through feeder, processing technology are as follows: an area
200 DEG C of temperature, two 200 DEG C of area's temperature, three 200 DEG C of area's temperature, four 200 DEG C of area's temperature, five 180 DEG C of area's temperature, head temperature 200
DEG C, 450 revs/min of engine speed.
Wherein, the ratio between spiro rod length L and diameter D L/D are 50, and screw rod is equipped with 3 gear block areas and 1 left-hand thread area.
The following are the raw materials of embodiment and comparative example to form list (table 1).
1 embodiment of table and comparative example raw material form parts by weight list
The low linear expansion coefficient halogen-free polypropylene flame redardant that above-described embodiment is prepared carries out following performance test:
Tensile property: GB/T 1040-2006 standard testing, rate of extension 50mm/min are pressed；
Impact property: GB/T1843-2008 standard testing is pressed, batten is with a thickness of 4mm；
Melt index: pressing GB/T 3682-2000 standard testing, and test temperature is 230 DEG C, loads as 2.16kg；
Flame retardant test: UL94 standard testing is pressed, batten is with a thickness of 2.0mm；
Linear expansion coefficient: pressing ISO11359 standard testing, and unit is 10-5 1/K.
The performance test results are as shown in table 2.
The performance list of the low linear expansion coefficient halogen-free anti-flaming polypropylene material of 2 embodiment of table and comparative example
Examples 1 to 7 is the additive amount for adjusting PP, compatilizer, halogen-free flame retardants, beta-eucryptite premix, promotor, from
It can be seen that the increase with beta-eucryptite premix additive amount, low linear expansion coefficient halogen-free anti-flaming polypropylene material in table
Linear expansion coefficient gradually decrease, and tensile strength, impact strength and melt index change are little, and flame retardant property can reach
To V-0 rank, linear expansion coefficient reaches most when wherein beta-eucryptite additive amount is 15 parts, compatilizer additive amount is 8 parts
Small value.By comparison, the comprehensive performance of embodiment 7 is best, and linear expansion coefficient reaches minimum value.
For embodiment 7 compared with comparative example 1, comparative example 1 does not add beta-eucryptite, but is added to the glass fibers of equivalent
Dimension illustrates that adding beta-eucryptite has lower linear expansion coefficient and superior flame retardant property than addition glass fibre；
Embodiment 7 does not add beta-eucryptite compared with comparative example 2, but is added to the wollastonite of equivalent, mechanical property, linear
The coefficient of expansion and flame retardant property are also poor compared to embodiment 7, illustrate that beta-eucryptite more has than wollastonite in linear expansion coefficient
Advantage has higher synergistic effect with piperazine halogen-free flameproof；Embodiment 7 does not add beta-eucryptite compared with comparative example 3,
But it is added to the talcum powder of equivalent, mechanical property, linear expansion coefficient and flame retardant property are also poor compared to embodiment 7,
It is more with the obvious advantage in linear expansion coefficient than talcum powder to illustrate beta-eucryptite, while talcum powder is not cooperateed with piperazine halogen-free flame retardants
Fire retardation；Embodiment 7 does not add beta-eucryptite compared with comparative example 4, but is added to the whisker of equivalent, mechanical property
Can quite, but linear expansion coefficient and flame retardant property are poor compared to embodiment 7, illustrate beta-eucryptite than whisker in linear expansion
Advantageously, whisker and piperazine halogen-free flame retardants are also acted on without cooperative flame retardant coefficient.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (9)
1. a kind of low linear expansion coefficient halogen-free flame-retardant polypropylene composition, it is characterised in that: by the raw material system of following parts by weight
It is standby to form:
The eucryptite premix is the premix of beta-eucryptite and titanate esters inorganic agent.
2. low linear expansion coefficient halogen-free anti-flaming polypropylene material according to claim 1, it is characterised in that: described is poly-
Allyl resin is copolymer polypropylene, and melt index 2-15g/10min, testing standard is GB/T 3682-2000, test temperature
It is 230 DEG C, loads as 2.16kg.
3. low linear expansion coefficient halogen-free anti-flaming polypropylene material according to claim 1, it is characterised in that: the phase
Appearance agent is maleic anhydride grafted ethene octene copolymer.
4. low linear expansion coefficient halogen-free anti-flaming polypropylene material according to claim 1, it is characterised in that: the nothing
Halogen fire retardant is piperazine pyrophosphate system fire retardant.
5. low linear expansion coefficient halogen-free anti-flaming polypropylene material according to claim 1, it is characterised in that: the rush
It is at least one of triallyl cyanurate, Triallyl isocyanurate or several into agent.
6. low linear expansion coefficient halogen-free anti-flaming polypropylene material according to claim 1, it is characterised in that: the master
Antioxidant is Hinered phenols antioxidant, and auxiliary anti-oxidant is phosphite ester antioxidant, and lubricant is the sour glycerine of single 18 (alkane)
Ester.
7. the preparation method of low linear expansion coefficient halogen-free anti-flaming polypropylene material described in -6 according to claim 1, feature
Be: described method includes following steps:
(1) eucryptite is placed in baking oven at 100~120 DEG C it is 3~5 hours dry, after cooling, by beta-eucryptite with 2%
100 DEG C of titanate coupling agent, temperature, 1000~1500 revs/min of mixed at high speed of revolving speed handle 5min, beta-eucryptite are prepared
Premix；
(2) raw material is weighed by weight ratio；
(3) by weighed each raw material mixed at high speed 2min, 80 DEG C of temperature, 1000 revs/min of revolving speed add to double after mixing
Screw extruder, processing technology are as follows: 180~200 DEG C of area's temperature, two 180~200 DEG C of area's temperature, three area's temperature 180~200
DEG C, four 180~200 DEG C of area's temperature, five 170~180 DEG C of area's temperature, 180~200 DEG C of head temperature, engine speed 400~500
Rev/min；
(4) water cooling, drying, pelletizing are after squeezing out to get low linear expansion coefficient halogen-free anti-flaming polypropylene material.
8. the preparation method of low linear expansion coefficient halogen-free anti-flaming polypropylene material according to claim 7, feature exist
In: the screw configuration of the double screw extruder is single thread；The ratio between spiro rod length L and diameter D L/D are 35~60；It is described
Screw rod is equipped with 1 or more gear block area and 1 or more left-hand thread area.
9. the preparation method of low linear expansion coefficient halogen-free anti-flaming polypropylene material according to claim 7, feature exist
In: the ratio between described spiro rod length L and diameter D L/D is 40~50；The screw rod is equipped with 3 gear block areas and 1 left-hand thread
Area.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910806426.9A CN110467777A (en) | 2019-08-29 | 2019-08-29 | A kind of low linear expansion coefficient halogen-free anti-flaming polypropylene material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910806426.9A CN110467777A (en) | 2019-08-29 | 2019-08-29 | A kind of low linear expansion coefficient halogen-free anti-flaming polypropylene material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110467777A true CN110467777A (en) | 2019-11-19 |
Family
ID=68513878
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910806426.9A Pending CN110467777A (en) | 2019-08-29 | 2019-08-29 | A kind of low linear expansion coefficient halogen-free anti-flaming polypropylene material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110467777A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111004445A (en) * | 2019-12-24 | 2020-04-14 | 清远市普塞呋磷化学有限公司 | Low-warpage UL94-5 VA-grade halogen-free flame-retardant polypropylene material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016222806A (en) * | 2015-05-29 | 2016-12-28 | 大日防蝕化工株式会社 | Multifunctional hybrid material, and machine and building component using the same |
| CN106317607A (en) * | 2015-06-18 | 2017-01-11 | 合肥杰事杰新材料股份有限公司 | Ultralow-linear expansion coefficient polypropylene composite material and preparation method thereof |
| CN107474383A (en) * | 2017-08-21 | 2017-12-15 | 广东圆融新材料有限公司 | A kind of halogen-free polypropylene flame redardant of high-temp resisting high-humidity resisting and lower shrinkage and preparation method thereof |
| CN108586933A (en) * | 2018-05-11 | 2018-09-28 | 苏州润佳工程塑料股份有限公司 | A kind of low-shrinkage polypropylene composite and preparation method thereof |
| CN109503941A (en) * | 2018-11-02 | 2019-03-22 | 广东圆融新材料有限公司 | Halogen-free anti-flaming polypropylene material and preparation method thereof |
-
2019
- 2019-08-29 CN CN201910806426.9A patent/CN110467777A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016222806A (en) * | 2015-05-29 | 2016-12-28 | 大日防蝕化工株式会社 | Multifunctional hybrid material, and machine and building component using the same |
| CN106317607A (en) * | 2015-06-18 | 2017-01-11 | 合肥杰事杰新材料股份有限公司 | Ultralow-linear expansion coefficient polypropylene composite material and preparation method thereof |
| CN107474383A (en) * | 2017-08-21 | 2017-12-15 | 广东圆融新材料有限公司 | A kind of halogen-free polypropylene flame redardant of high-temp resisting high-humidity resisting and lower shrinkage and preparation method thereof |
| CN108586933A (en) * | 2018-05-11 | 2018-09-28 | 苏州润佳工程塑料股份有限公司 | A kind of low-shrinkage polypropylene composite and preparation method thereof |
| CN109503941A (en) * | 2018-11-02 | 2019-03-22 | 广东圆融新材料有限公司 | Halogen-free anti-flaming polypropylene material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 徐克勋主编: "《辽宁省化工产品手册》", 28 April 1988 * |
| 李懋强编著: "《热学陶瓷——性能•测试•工艺》", 30 June 2013, 中国建材工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111004445A (en) * | 2019-12-24 | 2020-04-14 | 清远市普塞呋磷化学有限公司 | Low-warpage UL94-5 VA-grade halogen-free flame-retardant polypropylene material and preparation method thereof |
| CN111004445B (en) * | 2019-12-24 | 2022-06-07 | 清远市普塞呋磷化学有限公司 | Low-warpage UL94-5 VA-grade halogen-free flame-retardant polypropylene material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103435887B (en) | A kind of high workability halide-free fireproof composite polyolefine material and preparation method thereof | |
| CN103382302B (en) | A kind of red phosphorus flame-retardant nylon composite and preparation method thereof | |
| CN111961331B (en) | Flame-retardant waterproof thermoplastic polyurethane elastomer cable material and preparation method thereof | |
| CN112250935A (en) | High-flame-retardant-grade low-smoke halogen-free material and preparation method and application thereof | |
| CN103087518B (en) | Glass-fiber-reinforced halogen-free flame-retardant nylon 46 composite material and preparation method thereof | |
| CN110591335A (en) | High-flame-retardance low-smoke-toxicity weather-resistant cable sheath material and preparation method thereof | |
| CN110643138B (en) | Modified flame-retardant ABS material and preparation method thereof | |
| CN111087690B (en) | Flame-retardant polypropylene composite material with electromagnetic shielding effect and scratch resistance and preparation method thereof | |
| CN103342880B (en) | A kind of high finish surface environment friendly halogen-free fireproof PBT composite and preparation method thereof | |
| CN109503941A (en) | Halogen-free anti-flaming polypropylene material and preparation method thereof | |
| CN114702749A (en) | Flame-retardant polyolefin and preparation method thereof | |
| CN110042528A (en) | A kind of shading fabric and preparation method thereof | |
| CN102040810A (en) | Polybutylece terephthalate (PBT) engineering plastics as well as preparation method and application thereof | |
| CN112442227B (en) | Low-smoke halogen-free cable material and preparation method and application thereof | |
| CN102367317A (en) | Flame retardant polypropylene (PP) material and its preparation method | |
| CN105111729B (en) | Environmental protection flame retardant carbon fiber reinforced polyamide composite material and its preparation method and application | |
| CN110467777A (en) | A kind of low linear expansion coefficient halogen-free anti-flaming polypropylene material and preparation method thereof | |
| CN110698805B (en) | Modified flame-retardant engineering plastic | |
| CN108034126B (en) | Halogen-free flame-retardant polyolefin composite material and preparation method thereof | |
| CN112322020B (en) | Polyphenyl ether resin composition and preparation method thereof, and wire slot and preparation method thereof | |
| CN103709663A (en) | Modified PET/PBT alloy material | |
| CN114213827A (en) | Solvent-resistant halogen-free flame-retardant PC/PETG alloy and preparation method thereof | |
| CN102604212B (en) | Aramid fiber pulp-enhanced expansion flame retardant polypropylene composite material and preparation method thereof | |
| CN115895206B (en) | Flame-retardant PET material and preparation method thereof | |
| CN1300238C (en) | Magnesium solt whisker rein forced fire-resisting polypropylene composition |
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 |
Application publication date: 20191119 |
|
| RJ01 | Rejection of invention patent application after publication |