CN103289193B - Continuous basalt fiber strengthens anti-flaming polypropylene material and preparation method thereof - Google Patents
Continuous basalt fiber strengthens anti-flaming polypropylene material and preparation method thereof Download PDFInfo
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- CN103289193B CN103289193B CN201310192031.7A CN201310192031A CN103289193B CN 103289193 B CN103289193 B CN 103289193B CN 201310192031 A CN201310192031 A CN 201310192031A CN 103289193 B CN103289193 B CN 103289193B
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Abstract
The invention discloses a kind of continuous basalt fiber and strengthen anti-flaming polypropylene material and preparation method thereof, material is mainly blended by 40 ~ 75wt.% continuous basalt fiber RPP master batch and 25 ~ 40% fire-retardant master granules and forms；Wherein continuous basalt fiber RPP master batch is mainly made up of 40 ~ 55wt.% continuous basalt fiber, 40 ~ 54 wt.% acrylic resins and 2 ~ 5 wt.% polar monomer graft polymeric compatibilizers；Fire-retardant master granule is mainly made up of 15 ~ 39 wt.% vistanexes, 45 ~ 63wt.% fire retardant and 14 ~ 21 wt.% fire retarding synergists；At least one during wherein fire retardant is TDE, decabromodiphenyl oxide and decabromodiphenyl, fire retarding synergist is stibium trioxide.Products obtained therefrom of the present invention not only has that good fire resistance, good mechanical performance, and preparation technology be simple, with low cost, environmental friendliness, meets industrialized production and the requirement to environmental protection, has wide market application foreground.
Description
Technical field
The present invention relates to a kind of fiber-reinforced polymer material and preparation method thereof, particularly relate to a kind of continuous basalt fine
Dimension strengthens anti-flaming polypropylene material and preparation method thereof, belongs to modified polypropylene composite material technical field.
Background technology
Basalt is as a kind of volcanic rock, and it is to form through High Temperature High Pressure and very long historical development in earth depths
's.Basalt is made watt by casting process and plate is for construction market history the most for many years, the basalt inner lining of steel pipe of casting
Having the highest wearability, be widely used in commercial production, basalt is also used as concrete under pulverizing state in addition
Gather materials.
Use the continuous fiber of natural refractory basalt extrusion, may serve to substitute stone in terms of almost all of purposes
Cotton fiber.Nearly ten years, basalt fibre has become the competitive material strengthening composite, itself and carbon fiber, aramid fiber, superelevation
The high technical fibre such as molecular weight polyethylene fiber (UHMWPE) are compared, except having the high intensity of high technical fibre and high-modulus
Outside feature, also have that heat-resisting quantity is good, antioxidation good, radioprotective is good, thermal acoustic insulation effect is good, filterability good, incompressible intensity
High with shear strength, be adapted under various environment the excellent properties such as use, and cost performance is good, is the inorganic non-gold of a kind of pure natural
Belong to material, be also a kind of novel foundation material that can meet infrastructural industry for the national economy growth requirement and high technical fibre.
Polypropylene (PP), as a kind of general-purpose plastics, enters each corner of daily life, wherein through E glass fibre
Modified PP material, by its good rigidity, instead of engineering plastics in certain applications.And the appearance of basalt fibre, enter
One step improves the room for promotion of polypropylene material performance, and basalt fibre has more surface activity site simultaneously, permissible
Improve the combination property of material to a greater extent.Along with the research of continuous basalt fiber is deepened day by day, application is also to engineering
Plastics are close, and its fire resistance will become an important index request.Therefore, study fire-retardant continuous basalt fiber to strengthen
Polymeric material be of great immediate significance and necessity.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the invention provides a kind of continuous basalt fiber and strengthen resistance
Combustion polypropylene material and preparation method thereof, the material comprehensive mechanical property that the method uses mixing method to produce has excellence, environmental protection
Reliably, and method high-efficient simple, with low cost, easily controllable.
The present invention is to solve that its technical problem be the technical scheme is that
A kind of continuous basalt fiber strengthens anti-flaming polypropylene material, mainly by 40～75wt.% continuous basalt fibers
RPP master batch and 25～40% fire-retardant master granule blend form；Wherein said continuous basalt fiber RPP master batch
Main by 40～55wt.% continuous basalt fibers, 40～54wt.% acrylic resin and 2～5wt.% polar monomer grafts
Polymeric compatibilizer forms；Described fire-retardant master granule is mainly by 15～39wt.% vistanexes, 45～63wt.% fire retardant
With 14～21wt.% fire retarding synergist compositions；Wherein said fire retardant is TDE, decabromodiphenyl oxide and decabromodiphenyl
In at least one, described fire retarding synergist is stibium trioxide.
Its further technical scheme is:
Described fire retardant is preferably TDE.
Described continuous basalt fiber strengthens anti-flaming polypropylene material and also includes the acrylic resin of scalable amount.
Described continuous basalt fiber RPP master batch and described fire-retardant master granule the most also include the thermally-stabilised of dosage
Agent and the lubricant of dosage.
Vistanex in described fire-retardant master granule is that melt index is more than 20g/ under 2.16kg/230 DEG C of test condition
The polypropylene of 10min, under 1.90kg/230 DEG C of test condition, melt index is divided more than the polyethylene of 20g/10min and molecular weight
Cloth curve presents no less than at least one in the polyethylene at two peaks.
Polymer in described polar monomer graft polymeric compatibilizer is polyethylene, polypropylene, Ethylene/Butylene copolymerization
At least one in thing and ethylene-octene copolymer, preferably polypropylene；Described polar monomer be maleic anhydride, acrylic acid and
At least one in acrylate, preferably maleic anhydride.Described polar monomer graft polymeric compatibilizer is preferably Malaysia
Anhydride-grafted polypropylene.
Present invention also offers a kind of continuous basalt fiber and strengthen the preparation method of anti-flaming polypropylene material, the method bag
Include following steps:
(1) preparation of continuous basalt fiber RPP master batch: by 40～54% acrylic resin, 2～5wt.%
The lubricant of polar monomer graft polymeric compatibilizer, the heat stabilizer of dosage and dosage feeding from double screw extruder
Material mouth adds, and carries out the most melted and mix homogeneously, is then drawn from die head especially used by 40～55wt.% continuous basalt fibers
After going out, sequentially pass through cold water but, pelleter pelletize, obtain a length of 5～12mm continuous basalt fiber RPP female
Grain；
(2) preparation of fire-retardant master granule: by 15～39wt.% vistanexes, 45～63wt.% fire retardant, 14～
In the banburying chamber of the lubricant addition banbury of 21wt.% fire retarding synergist, the heat stabilizer of dosage and dosage, mixing is all
Even and melt pelletization, obtains fire-retardant master granule；
(3) by obtained flame-retardant master batch in gained continuous basalt fiber RPP master batch, (2) in (1), regulated quantity
Acrylic resin obtains continuous basalt fiber and strengthens anti-flaming polypropylene material, wherein continuous basalt after mixing in proportion
TRPP master batch accounts for continuous basalt fiber and strengthens the 40～75wt.% of fire-retardant nylon material, and fire-retardant master granule accounts for even
Continuous basalt fibre strengthens the 25～40wt.% of fire-retardant nylon material, and continuous basalt fiber accounts for continuous basalt fiber and increases
The 20～37.5wt.% of strong anti-flaming polypropylene material.
The method have the benefit that: the present invention is by continuous basalt fiber RPP master batch and fire-retardant master granule
Blending in proportion and form, can add the acrylic resin content with regulation basalt fibre with fire retardant simultaneously, products obtained therefrom is not
Only have that good fire resistance, good mechanical performance, and preparation technology be simple, with low cost, environmental friendliness, meet industrialization
Production and the requirement to environmental protection, have wide market application foreground.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail, and following embodiment is merely to illustrate this
Bright, it is not limiting as the present invention.
Embodiment 1
The preparation of continuous basalt fiber RPP master batch:
By acrylic resin HJ4045 (melt index 45g/10min), the polar monomer graft polymer-type of 4% of 45%
Compatibilizer C A100 (maleic anhydride inoculated polypropylene), 1% heat stabilizer (dilauryl thiodipropionate and 4-hydroxyoctadecanoic
Anilid presses 1:1 mixing) after mix homogeneously, use dipping die head, continuous basalt fiber is pulled through dipping die head, is prepared as
Continuous basalt fiber RPP master batch, the content of continuous basalt fiber is 50%.
The preparation of fire-retardant master granule:
By 15% polypropylene PP 320 powder (melt index 37g/10min), 63% TDE, 21% stibium trioxide and
1% heat stabilizer (4-hydroxyoctadecanoic anilid is mixed by 1:1 with triphenyl phosphite) is mixed homogeneously, molten in banbury
Melt pelletize, obtain required fire-retardant master granule.
The preparation of continuous basalt fiber enhancing anti-flaming polypropylene material:
Continuous basalt fiber RPP master batch, fire-retardant master granule and acrylic resin K1011 are pressed 2:2:1 mixing,
Prepare required continuous basalt fiber and strengthen anti-flaming polypropylene material.In final composite, polypropylene content is
44%, polar monomer graft polymeric compatibilizer content is 1.6%, and continuous basalt fiber content is 20%, heat stabilizer
Content is 0.8%, and TDE content is 25.2%, and fire retarding synergist stibium trioxide content is 8.4%, the above
Percentage composition is all weight percentage.
Embodiment 2
The preparation of continuous basalt fiber RPP master batch:
With embodiment 1；
The preparation of fire-retardant master granule:
By 39% bimodal polyethylene FB2230,45% TDE, 15% stibium trioxide and 1% heat stabilizer (4-hydroxyl
Octadecane anilid is mixed by 1:1 with triphenyl phosphite) mix homogeneously, melt pelletization in banbury, obtain required
Fire-retardant master granule.
The preparation of continuous basalt fiber enhancing fire-retardant nylon material:
Continuous basalt fiber RPP master batch is mixed by 1:1 with fire-retardant master granule, prepares required the most profound
Military rock fiber reinforcement anti-flaming polypropylene material.In final composite, polypropylene content is 22.5%, and bimodal polyethylene contains
Amount 19.5%, polar monomer graft polymeric compatibilizer content is 2%, and continuous basalt fiber content is 25%, thermally-stabilised
Agent content is 1%, and TDE content is 22.5%, and fire retarding synergist stibium trioxide content is 7.5%, the above
Percentage composition is all weight percentage.
Embodiment 3
The preparation of continuous basalt fiber RPP master batch:
With embodiment 1；
The preparation of fire-retardant master granule:
With embodiment 1；
The preparation of continuous basalt fiber enhancing fire-retardant nylon material:
Continuous basalt fiber RPP master batch is mixed by 3:1 with fire-retardant master granule, prepares required the most profound
Military rock fiber reinforcement anti-flaming polypropylene material.In final composite, polypropylene content is 37.5%, polar monomer graft
Polymeric compatibilizer content is 3%, and continuous basalt fiber content is 37.5%, and heat stabilizer content is 1%, fire retardant ten
Bromine diphenylethane content is 15.75%, and fire retarding synergist stibium trioxide content is 5.25%, and the above percentage composition is weight hundred
Proportion by subtraction.
Embodiment 4
The preparation of continuous basalt fiber RPP master batch:
By acrylic resin K7760 (melt index 60g/10min), the polar monomer graft polymer-type of 5% of 54%
(triphenyl phosphite and 4-hydroxyoctadecanoic acyl are for benzene for Compatibilizer C A100 (maleic anhydride inoculated polypropylene), 1% heat stabilizer
Amine presses 3:1 mixing) after mix homogeneously, use dipping die head, continuous basalt fiber is pulled through dipping die head, is prepared as the most profound
Military rock TRPP master batch, the content of continuous basalt fiber is 40%.
The preparation of fire-retardant master granule:
With embodiment 2；
The preparation of continuous basalt fiber enhancing fire-retardant nylon material:
Continuous basalt fiber RPP master batch is mixed by 3:1 with fire-retardant master granule, prepares required the most profound
Military rock fiber reinforcement anti-flaming polypropylene material.In final composite, polypropylene content is 40.5%, and bimodal polyethylene contains
Amount 9.75%, polar monomer graft polymeric compatibilizer content is 3.75%, and continuous basalt fiber content is 30%, and heat is steady
Determining agent content is 1%, and TDE content is 11.25%, and fire retarding synergist stibium trioxide content is 3.75%, above
Described percentage composition is all weight percentage.
Embodiment 5
The preparation of continuous basalt fiber RPP master batch:
With embodiment 4；
The preparation of fire-retardant master granule:
By 27% linear low density polyethylene M500026 (melt index 40g/10min), 54% TDE,
18% stibium trioxide and 1% heat stabilizer (4-hydroxyoctadecanoic anilid is mixed by 1:1 with triphenyl phosphite) are mixed homogeneously,
Melt pelletization in banbury, obtains required fire-retardant master granule.
The preparation of continuous basalt fiber enhancing fire-retardant nylon material:
Continuous basalt fiber RPP master batch is mixed by 2:1 with fire-retardant master granule, prepares required the most profound
Military rock fiber reinforcement anti-flaming polypropylene material.In final composite, polypropylene content is 36%, polymerized ethylene content 9%,
Polar monomer graft polymeric compatibilizer content is 3.3%, and continuous basalt fiber content is 26.7%, heat stabilizer content
Being 1%, TDE content is 18%, and fire retarding synergist stibium trioxide content is 6%, and the above percentage composition is equal
It is weight percentage.
Embodiment 6
The preparation of continuous basalt fiber RPP master batch:
By acrylic resin HJ4045 (melt index 45g/10min), the polar monomer graft polymer-type of 2% of 40%
Compatibilizer C A100 (maleic anhydride inoculated polypropylene), 1.5% heat stabilizer (dilauryl thiodipropionate and 4-hydroxyl 18
Alkane anilid presses 1:1 mixing) and 1.5% mix lubricant uniformly after, use and impregnate die head, by 55% continuous basalt fiber
Being pulled through dipping die head, be prepared as continuous basalt fiber RPP master batch, the content of continuous basalt fiber is 55%.
The preparation of fire-retardant master granule:
By 35% polypropylene PP 320 powder (melt index 37g/10min), 50% TDE, 14% stibium trioxide,
0.5% heat stabilizer (4-hydroxyoctadecanoic anilid is mixed by 1:1 with triphenyl phosphite) and 0.5% mix lubricant are equal
Even, melt pelletization in banbury, obtain required fire-retardant master granule.
The preparation of continuous basalt fiber enhancing anti-flaming polypropylene material:
Continuous basalt fiber RPP master batch, fire-retardant master granule and acrylic resin K1011 are pressed 2:2:1 mixing,
Prepare required continuous basalt fiber and strengthen anti-flaming polypropylene material.In final composite, polypropylene content is
50%, polar monomer graft polymeric compatibilizer content is 0.8%, and continuous basalt fiber content is 22%, heat stabilizer
Content is 0.8%, and TDE content is 20%, and fire retarding synergist stibium trioxide content is 5.6%, and the above is hundred years old
Content is divided all to be weight percentage.
The performance detection data of the various embodiments described above resulting materials is as shown in table 1, and wherein mechanical test project is marked according to ISO
Standard is carried out, and is respectively as follows: hot strength ISO 527-2, bending strength and bending modulus ISO 178, notch impact strength ISO
180/1A, fire resistance UL94 standard, and in the various embodiments described above, heat stabilizer used and lubricant are product commonly used in the art
Product.
In the various embodiments described above, NM operational approach and process conditions etc. are well known to the skilled person
Technology contents, repeats no more in the present invention.
Table 1
Claims (6)
1. the preparation method of a continuous basalt fiber enhancing anti-flaming polypropylene material, it is characterised in that: comprise the following steps:
(1) preparation of continuous basalt fiber RPP master batch: total by continuous basalt fiber RPP master batch
Percentage by weight meter, by 40～54wt.% acrylic resins, 2～5wt.% polar monomer graft polymeric compatibilizer, dosage
Heat stabilizer and the lubricant of dosage add from the spout of double screw extruder, carry out the most melted and mix homogeneously,
Then, by 40～55wt.% continuous basalt fibers after die head especially used middle pull-out, water cooling, pelleter pelletize are sequentially passed through,
To the continuous basalt fiber RPP master batch of a length of 5～12mm；
(2) preparation of fire-retardant master granule: based on the total weight percent of fire-retardant master granule, by 15～39wt.% vistanexes, 45～
The lubricant of 63wt.% fire retardant, 14～21wt.% fire retarding synergist, the heat stabilizer of dosage and dosage adds banbury
Banburying chamber in mix homogeneously melt pelletization, obtain fire-retardant master granule；
(3) by obtained flame-retardant master batch in gained continuous basalt fiber RPP master batch, (2) in (1), poly-the third of conciliation amount
Olefine resin obtains continuous basalt fiber and strengthens anti-flaming polypropylene material, wherein continuous basalt fiber after mixing in proportion
RPP master batch accounts for continuous basalt fiber and strengthens the 40～75wt.% of anti-flaming polypropylene material, and fire-retardant master granule accounts for the most profound
The 25～40wt.% of military rock fiber reinforcement anti-flaming polypropylene material, and continuous basalt fiber accounts for continuous basalt fiber and strengthens resistance
The 20～37.5wt.% of combustion polypropylene material.
Continuous basalt fiber the most according to claim 1 strengthens the preparation method of anti-flaming polypropylene material, and its feature exists
In: described in step (1), the polymer in polar monomer graft polymeric compatibilizer is polyethylene, polypropylene, Ethylene/Butylene
At least one in copolymer and ethylene-octene copolymer, described polar monomer is in maleic anhydride, acrylic acid and acrylate
At least one.
Continuous basalt fiber the most according to claim 2 strengthens the preparation method of anti-flaming polypropylene material, and its feature exists
In: described in step (1), polar monomer graft polymeric compatibilizer is maleic anhydride inoculated polypropylene.
Continuous basalt fiber the most according to claim 1 strengthens the preparation method of anti-flaming polypropylene material, and its feature exists
In: described in step (2), fire retardant is at least one in TDE, decabromodiphenyl oxide and decabromodiphenyl, described resistance
Combustion synergist is stibium trioxide.
Continuous basalt fiber the most according to claim 4 strengthens the preparation method of anti-flaming polypropylene material, and its feature exists
In: described in step (2), fire retardant is TDE.
Continuous basalt fiber the most according to claim 1 strengthens the preparation method of anti-flaming polypropylene material, and its feature exists
In: the vistanex in fire-retardant master granule described in step (2) is more than for melt index under 2.16kg/230 DEG C of test condition
The polypropylene of 20g/10min, under 1.90kg/230 DEG C of test condition melt index more than the polyethylene of 20g/10min and molecule
Amount distribution curve presents no less than at least one in the polyethylene at two peaks.
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Families Citing this family (3)
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| CN105086136A (en) * | 2015-07-30 | 2015-11-25 | 南京京锦元科技实业有限公司 | Preparation method of continuous basalt fiber reinforced flame-retardant PP master batch |
| CN105733091A (en) * | 2015-07-30 | 2016-07-06 | 南京京锦元科技实业有限公司 | High-fiber-content continuous basalt fiber reinforced flame-retarding PP master batch and application thereof |
| CN110862606A (en) * | 2019-11-08 | 2020-03-06 | 重庆永高塑业发展有限公司 | Production method of basalt reinforced modified polypropylene cable guide |
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| CN102850816A (en) * | 2011-06-27 | 2013-01-02 | 上海杰事杰新材料(集团)股份有限公司 | Thermoplastic resin composite material and preparation method and application thereof |
| CN102942737A (en) * | 2012-10-30 | 2013-02-27 | 上海金发科技发展有限公司 | Basalt fiber-reinforced environmental-friendly flame-retardant polypropylene composite material and preparation method thereof |
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- 2013-05-22 CN CN201310192031.7A patent/CN103289193B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102260413A (en) * | 2010-05-28 | 2011-11-30 | 合复新材料科技(无锡)有限公司 | Composite material component with high flame retardation performance and high heat conduction performance, and its manufacture method |
| CN102295792A (en) * | 2010-06-28 | 2011-12-28 | 辽宁杰事杰新材料有限公司 | Continuous fiber enhanced thermoplastic antiflaming presoaking belt composite material and preparation method thereof |
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