CN108359174A - Low bromine anti-flaming polypropylene composite of a kind of low smell and preparation method thereof - Google Patents
Low bromine anti-flaming polypropylene composite of a kind of low smell and preparation method thereof Download PDFInfo
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- CN108359174A CN108359174A CN201810118308.4A CN201810118308A CN108359174A CN 108359174 A CN108359174 A CN 108359174A CN 201810118308 A CN201810118308 A CN 201810118308A CN 108359174 A CN108359174 A CN 108359174A
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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
- C08L23/12—Polypropene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/14—Copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- 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
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses low bromine anti-flaming polypropylene composite of a kind of low smell and preparation method thereof, the low bromine anti-flaming polypropylene composite of the low smell is made of the raw material by following weight percent：Polypropylene (PP) 62% 90.6%, composite flame-retardant agent 3% 15%, toughener 5% 15%, eliminating smell agent 1% 5%, antioxidant 0.1% 1.5%, other processing aids 0.3% 1.5%.The low bromine anti-flaming polypropylene composite of low smell of the present invention has smell low, and oder levels 3.0 are hereinafter, flame retardant effect is excellent, 24 or more oxygen index (OI), flame retardant rating V2.It has greatly improved in the more traditional fire-retardant PP of smell, mechanical property, flame retardant property, can be widely applied to the low smell flame retardant products of automobile.Invention additionally discloses a kind of preparation methods of the low bromine anti-flaming polypropylene composite of low smell.
Description
Technical field
The invention belongs to macromolecule modified technical fields；It is related to a kind of low bromine anti-flaming polypropylene composite of low smell and its system
Preparation Method.
Background technology
Polypropylene (PP) has many advantages, such as excellent mechanical performance and good insulation performance, and density is small to be widely used in
Electronics, the fields such as electric appliance however, PP is readily burned, and discharge in burning a large amount of heat along with dripping phenomenon, it by with
Make electric material, be typically due to overheat, the reasons such as high pressure easily cause fire.As people are more next to the safety of environment and substance
More emphasize that research and development meet security against fire and the novel low halogen of environmental requirement or halogen-free flameproof PP is of great significance.FR6000 is one
The low bromine phosphonium flame retardant of money, bromine content is 6% hereinafter, it combines the mutually fire-retardant cohesion phase resistance with organophosphor of efficient air of bromine system
Combustion, is a kind of efficient fire retardant, and smell is relatively low, is very suitable for doing the low flame-retardant modified product of smell.
A type molecular sieve cell is by two octahedra compositions of Fourth Ring connection, and distinctive gap structure is by eight membered oxygen rings shapes
At aperture separate and to be formed, produced in technique at present it is ripe, it is cheap, the different aperture diameters such as 3A/4A/5A can be prepared
Molecular sieve, and the aperture diameter of 4A molecular sieves can adsorb a large amount of amine with the diameter matches of most of small molecules, sulphur
Class, thio-alcohol small-molecule substance；There is 4A molecular sieves good fire-retardant synergistic effect, 4A molecular sieves to make in phosphorus system organic phase simultaneously
Itself SiO is resolved into lower2And Al2O3, the generation of final Si-P-Al-C structures, play promote at charcoal and stablize at charcoal work
With, therefore be a kind of odor adsorption agent with flame retardant synergism.
Currently, the development of low smell polypropylene flame redardant, is concentrated mainly on by the way that adsorptivity clay, zeolite is added, chemistry removes
Taste agent etc. reduces the smell of polymer with Polypropylene copolymer modification.But these adsorbents often reduce flame retardant effect, make
It is subject to certain restrictions in.
Invention content
The present invention proposes a kind of low bromine anti-flaming polypropylene composite of low smell and its system to overcome the deficiencies of existing technologies
Preparation Method.
A kind of low bromine anti-flaming polypropylene composite of low smell of the present invention is made of the raw material of following weight percent：
The polypropylene is low smell homopolymerization PP, random copolymerization PP, at least one of block copolymerization PP, melt index
More than 10g/min；It is preferred that the K8003 of the T30S and the production of Siam of Thailand of Maoming Petrochemical production.
The composite flame-retardant agent is zinc borate/FR6000, compound proportion 1:(3-6), FR-6000 are a kind of novel height
Environmentally friendly P, N, Br compound system fire retardant of the response type of effect, for bromine content 6% hereinafter, high with flame retarding efficiency, smell is low
Feature is compounded with zinc borate, and oxygen index (OI) can be improved, and reduces smoke density.
The toughener is low smell POE, low density polyethylene (LDPE), at least one of POP.Preferably, low smell
POE。
The eliminating smell agent is 3A molecular sieves, 4A molecular sieves, at least one of 5A molecular sieves.Molecular sieve, which has, efficiently to be inhaled
Attached property, while the oxygen index (OI) of phosphorus system system can be improved.
The antioxidant is by primary antioxidant and auxiliary anti-oxidant 1:1 composition, wherein primary antioxidant are aromatic amine antioxidant,
One kind of Hinered phenols antioxidant, auxiliary anti-oxidant are thio-2 acid dibasic acid esters, one kind of phosphite ester.
Other described processing aids are lubricant TAF, calcium stearate, stearate acid zinc, one or more of silicone.
The present invention also provides a kind of preparation methods of the low bromine polypropylene flame redardant of low smell.Include the following steps：
(1) each raw material is added in high mixer by formula rate, is premixed 3-8 minutes, obtain mixed thing, discharging is spare；
(2) mixed thing is put into double screw extruder melting extrusion tie rod, particularly, is saved at cylinder in extruder second
The water for accounting for raw material gross mass 0.5%-6% is added；
(3) material strip is through supercooling, pelletizing, drying, obtains the low bromine anti-flaming polypropylene composite of low smell.
The water is RO water, and pure water, one kind in deionized water, water temperature is 30-60 DEG C.
The rotating speed of the double screw extruder is 250-450rpm, draw ratio 40/1, the feeding section of extruder to head
Temperature be 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C, 170 DEG C, double vacuum, vacuum degree is big
In 0.6MPa.
Stoving process is dried 16 hours for 80 DEG C in vertical drying oven.
The product of the present invention compared with prior art, has effect below：
It being compounded using low bromine phosphonium flame retardant FR6000 and zinc borate, obtained product has good flame retardant property,
When additive amount is 5%, oxygen index (OI) reaches 24, flame retardant rating V2, and meets ROHS environmental requirements.
Using low odorant materials and low smell fire retardant, smell is controlled from source；Pass through eliminating smell agent molecular sieve and extrusion again
In the process plus water proposes gas taste removal and baking step is combined to product taste removal, taste removal excellent effect, is tested according to automobile PV3900
Oder levels are 3.0.
Specific implementation mode
With reference to specific embodiment, the present invention is described in detail.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, non-limiting protection scope of the present invention.
Polypropylene used in embodiment is the one or two kinds of of T30S, K8003, composite flame-retardant agent be FR6000 and
Zinc borate carries out compounding in proportion, toughener POE, antioxidant 1010,168 compound, other auxiliary agents be amide waxe and
Calcium stearate compounds, and eliminating smell agent is 4A molecular sieves.
Constituent content is weight percentage in embodiment.
Preparation method：(1) each raw material is added in high mixer by formula rate, premixes 3-8 minutes, obtains mixed thing,
It discharges spare；
(2) mixed thing is put into double screw extruder melting extrusion tie rod, particularly, is saved at cylinder in extruder second
The RO water for accounting for raw material gross mass 0.5%-6% is added；
(3) material strip is through supercooling, pelletizing, drying, obtains the low bromine anti-flaming polypropylene material of low smell.
The rotating speed of the double screw extruder is 250-450rpm, draw ratio 40/1, the feeding section of extruder to head
Temperature be 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C, 170 DEG C, double vacuum, vacuum degree is big
In 0.6MPa.
Stoving process is dried 16 hours for 80 DEG C in vertical drying oven.
Testing standard：Extension test according to national standard GB/T1040, shock-testing according to national standard GB/T1043, crooked test according to
According to national standard GB/T9341, bending modulus test is tested according to national standard GB/T9341, oxygen index (OI) according to national standard GB/T 2406.1-
2009, GB/T 2406.2-2009, oder levels are tested according to automobile PV3900, and flame retardant rating is according to national standard GB/T 2408-
2008, using vertical burn test.
Each Example formulations and taste removal technique such as table 1.
1 each Example formulations of table and taste removal technique
Test result such as table 2
2 test result of table
In conjunction with table 1,2 as can be seen that this formula system is a flame retarding efficiency height, a low formula system of smell；
After special taste removal treatment process, oder levels decline apparent, oder levels 2.0, and oxygen index (OI) and flame retardant rating substantially not under
Drop considerably reduces the oder levels of product, has also kept basic mechanical while the present invention realizes promotion flame retardant property
Performance.And comparative example 1 does not pass through taste removal process, and eliminating smell agent is not added in formula yet, oder levels are not obviously higher by two
It is more than a grade.
The above content is only the preferred embodiments of the present invention, is to facilitate those skilled in the art it will be appreciated that and application
The present invention.Mentality of designing according to the present invention has change on it need not pass through creative specific example application range
Place.Therefore, the present invention should not be construed as the limitation to the specific example, all should in the change not departed from scope
Within the scope of the present invention.
Claims (10)
1. a kind of low bromine anti-flaming polypropylene composite of low smell, it is characterised in that：It is made of the raw material of following weight percent：
。
2. the low bromine anti-flaming polypropylene composite of a kind of low smell according to claim 1, which is characterized in that the polypropylene
For low smell homopolymerization PP, random copolymerization PP, at least one of block copolymerization PP, quality melt index is more than 10g/min, preferably
The P840J of the Z30S and the production of Siam of Thailand of Maoming Petrochemical production.
3. the low bromine anti-flaming polypropylene composite of a kind of low smell according to claim 1, which is characterized in that the compound resistance
Combustion agent is zinc borate/FR6000, compound proportion 1:(3~6)；The wherein described FR6000 is a kind of new and effective response type
Environmentally friendly P, N, Br compound system fire retardant, bromine content is below 6%.
4. the low bromine anti-flaming polypropylene composite of a kind of low smell according to claim 1, which is characterized in that the toughener
For POE, low density polyethylene (LDPE), preferably low smell POE.
5. the low bromine anti-flaming polypropylene composite of a kind of low smell according to claim 1, which is characterized in that the eliminating smell agent
For 3A molecular sieves, 4A molecular sieves, at least one of 5A molecular sieves.
6. the low bromine anti-flaming polypropylene composite of a kind of low smell according to claim 1, which is characterized in that the antioxidant
By primary antioxidant and auxiliary anti-oxidant 1:1 composition, wherein primary antioxidant be aromatic amine antioxidant, the one of Hinered phenols antioxidant
Kind, auxiliary anti-oxidant is thio-2 acid dibasic acid esters, one kind of phosphite ester.
7. the low bromine anti-flaming polypropylene composite of a kind of low smell according to claim 1, which is characterized in that other described add
Work auxiliary agent is lubricant TAF, calcium stearate, stearate acid zinc, one or more of silicone.
8. a kind of preparation method of the low bromine anti-flaming polypropylene composite of low smell, which is characterized in that carry out according to the following steps：
(1) each raw material is added in high mixer by formula rate, is premixed 3-8 minutes, obtain mixed thing, discharging is spare；
(2) mixed thing is put into double screw extruder melting extrusion tie rod, particularly, saves in extruder second and be added at cylinder
Account for the water of raw material gross mass 0.5%-6%；
(3) material strip is through supercooling, pelletizing, drying, obtains the low bromine anti-flaming polypropylene composite of low smell.
9. the preparation method of the low bromine anti-flaming polypropylene composite of a kind of low smell according to claim 8, which is characterized in that add
The water entered is RO water, and pure water, one kind in deionized water, water temperature is 30-60 DEG C.
10. the preparation method of the low bromine anti-flaming polypropylene composite of a kind of low smell according to claim 8, which is characterized in that
The rotating speed of the double screw extruder is 250-450rpm, and the temperature of draw ratio 40/1, feeding section to the head of extruder is
160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C, 170 DEG C, double vacuum, vacuum degree be more than-
0.6MPa。
Stoving process is dried 16 hours for 80 DEG C in vertical drying oven.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810118308.4A CN108359174A (en) | 2018-02-06 | 2018-02-06 | Low bromine anti-flaming polypropylene composite of a kind of low smell and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810118308.4A CN108359174A (en) | 2018-02-06 | 2018-02-06 | Low bromine anti-flaming polypropylene composite of a kind of low smell and preparation method thereof |
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| CN108359174A true CN108359174A (en) | 2018-08-03 |
Family
ID=63004655
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810118308.4A Pending CN108359174A (en) | 2018-02-06 | 2018-02-06 | Low bromine anti-flaming polypropylene composite of a kind of low smell and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110713657A (en) * | 2019-11-08 | 2020-01-21 | 江苏沃特新材料科技有限公司 | Polypropylene composite flame-retardant material for vehicle interior trim and preparation method and application thereof |
| CN111333951A (en) * | 2020-03-09 | 2020-06-26 | 南通大学 | Low-smoke halogen-free flame-retardant automobile foot mat material and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110713657A (en) * | 2019-11-08 | 2020-01-21 | 江苏沃特新材料科技有限公司 | Polypropylene composite flame-retardant material for vehicle interior trim and preparation method and application thereof |
| CN111333951A (en) * | 2020-03-09 | 2020-06-26 | 南通大学 | Low-smoke halogen-free flame-retardant automobile foot mat material and preparation method thereof |
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Application publication date: 20180803 |