CN103289193A - Continuous basalt fiber-reinforced flame-retardant polypropylene material and preparation method thereof - Google Patents
Continuous basalt fiber-reinforced flame-retardant polypropylene material and preparation method thereof Download PDFInfo
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- CN103289193A CN103289193A CN2013101920317A CN201310192031A CN103289193A CN 103289193 A CN103289193 A CN 103289193A CN 2013101920317 A CN2013101920317 A CN 2013101920317A CN 201310192031 A CN201310192031 A CN 201310192031A CN 103289193 A CN103289193 A CN 103289193A
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Abstract
The invention discloses a continuous basalt fiber-reinforced flame-retardant polypropylene material and a preparation method thereof. The continuous basalt fiber-reinforced flame-retardant polypropylene material is prepared by mainly mixing the following components in percentage by weight: 40%-75% of continuous basalt fiber-reinforced polypropylene master batches and 25%-40% of flame-retardant master batches, wherein each continuous basalt fiber-reinforced polypropylene master batch mainly comprises the following components in percentage by weight: 40%-55% of continuous basalt fibers, 40%-54% of polypropylene resin and 2%-5% of polar monomer graft polymer type compatilizers; each flame-retardant master batch mainly comprises the following components in percentage by weight: 15%-39% of polyolefin resin, 45%-63% of fire retardants and 14%-21% of flame-retardant synergists; the fire retardants are at least one of decabromodiphenylethane, decabromodiphenyl ether and decabromobiphenyl; the flame-retardant synergists are antimony white. The obtained product has the advantages of good fire-retardant property, excellent mechanical property, simple preparation process, low cost, environmental friendliness and wide market application prospect and meets the requirements for industrialized production, green and environmental friendliness.
Description
Technical field
The present invention relates to a kind of fiber-reinforced polymer material and preparation method thereof, relate in particular to a kind of continuous basalt fiber and strengthen anti-flaming polypropylene material and preparation method thereof, belong to the modified polypropylene composite material technical field.
Background technology
Basalt is as a kind of volcanics, and it is to form through High Temperature High Pressure and very long historical development in earth depths.Basalt is made watt by casting process and plate to be used for construction market existing historical for many years, the basalt inner lining of steel pipe of casting has very high wear resistance, is widely used in the industrial production, basalt can also be used as concrete gathering materials under the pulverizing state in addition.
The continuous fibre that adopts natural fire-resistant basalt to extrude can be used for substituting fibrous magnesium silicate aspect nearly all purposes.Over past ten years, basalt fibre has become the competitive material of reinforced composite, itself and carbon fiber, aramid fiber, superhigh molecular weight polyethylene fibers hi-tech fibers such as (UHMWPE) is compared, except the characteristics of high strength with hi-tech fiber and high-modulus, it is good also to have high thermal resistance, anti-oxidant good, radioprotective is good, adiabatic soundproof effect is good, filterableness is good, incompressible intensity and shearing resistance height, be adapted to excellent properties such as use under the various environment, and cost performance is good, being a kind of ceramic of pure natural, also is a kind of novel foundation material and hi-tech fiber that can satisfy foundation of national economy industry development demand.
Polypropylene (PP) has entered each corner of daily life as a kind of general-purpose plastics, and wherein the PP material through the modification of E glass fibre relies on its favorable rigidity, has replaced engineering plastics in certain applications.And the appearance of basalt fibre has further promoted the room for promotion of polypropylene material performance, and basalt fibre has more surfactivity site simultaneously, can be in the over-all properties that improves material to a greater extent.Along with the research of continuous basalt fiber is deepened day by day, to use also closely to engineering plastics, its flame retardant properties will become an important index requirement.Therefore, the polymer materials that strengthens of the fire-retardant continuous basalt fiber of research is 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 anti-flaming polypropylene material and preparation method thereof, the material comprehensive mechanical property that this method adopts hybrid system to produce has excellence, environmental protection reliable, and the method high-efficient simple, with low cost, be easy to control.
The present invention for the technical scheme that solves its technical problem and adopt is:
A kind of continuous basalt fiber strengthens anti-flaming polypropylene material, is mainly formed by 40 ~ 75wt.% continuous basalt fiber Reinforced Polypropylene master batch and 25 ~ 40% fire-retardant master granule blending; Wherein said continuous basalt fiber Reinforced Polypropylene master batch mainly is made up of 40 ~ 55wt.% continuous basalt fiber, 40 ~ 54 wt.% acrylic resins and 2 ~ 5 wt.% polar monomer graftomer type compatilizers; Described fire-retardant master granule mainly is made up of 15 ~ 39 wt.% polyolefin resines, 45 ~ 63wt.% fire retardant and 14 ~ 21 wt.% fire retarding synergists; Wherein said fire retardant is at least a in TDE, decabromodiphenyl oxide and the decabromodiphenyl, and described fire retarding synergist is stibium trioxide.
Its further technical scheme is:
Described fire retardant is preferably TDE.
But described continuous basalt fiber strengthens the acrylic resin that anti-flaming polypropylene material also comprises regulated quantity.
Described continuous basalt fiber Reinforced Polypropylene master batch and described fire-retardant master granule all also comprise the thermo-stabilizer of dosage and the lubricant of dosage.
Polyolefin resin in the described fire-retardant master granule in melting index under the 2.16kg/230 ℃ of test condition greater than the polypropylene of 20g/10min, melting index presents at least a in the polyethylene that is no less than two peaks greater than the polyethylene of 20g/10min and molecular weight distribution curve under 1.90 kg/230 ℃ test condition.
Polymkeric substance in the described polar monomer graftomer type compatilizer is at least a in polyethylene, polypropylene, ethylene-butene copolymer and the ethylene-octene copolymer, is preferably polypropylene; Described polar monomer is at least a in maleic anhydride, vinylformic acid and the acrylate, is preferably maleic anhydride.Described polar monomer graftomer type compatilizer is preferably maleic anhydride inoculated polypropylene.
The present invention also provides a kind of continuous basalt fiber to strengthen the preparation method of anti-flaming polypropylene material, and this method may further comprise the steps:
(1) preparation of continuous basalt fiber Reinforced Polypropylene master batch: the lubricant of the thermo-stabilizer of 40 ~ 54% acrylic resins, 2 ~ 5wt.% polar monomer graftomer type compatilizer, dosage and the dosage spout from twin screw extruder is added, carry out abundant fusion and mix, after then 40 ~ 55wt.% continuous basalt fiber being pulled out from die head especially used, successively through supercooled water but, the dicing machine granulation, obtaining length is the continuous basalt fiber Reinforced Polypropylene master batch of 5 ~ 12mm;
(2) preparation of fire-retardant master granule: the lubricant of the thermo-stabilizer of 15 ~ 39 wt.% polyolefin resines, 45 ~ 63 wt.% fire retardants, 14 ~ 21 wt.% fire retarding synergists, dosage and dosage is added in the banburying chamber of Banbury mixer and mix and melt pelletization, get fire-retardant master granule;
(3) obtain continuous basalt fiber after the acrylic resin of obtained flame-retardant master batch, regulated quantity in gained continuous basalt fiber Reinforced Polypropylene master batch, (2) in (1) is mixed in proportion and strengthen anti-flaming polypropylene material, wherein continuous basalt fiber Reinforced Polypropylene master batch accounts for 40 ~ 75wt.% that continuous basalt fiber strengthens fire-retardant nylon material, fire-retardant master granule accounts for 25 ~ 40wt.% that continuous basalt fiber strengthens fire-retardant nylon material, and continuous basalt fiber accounts for 20 ~ 37.5wt.% that continuous basalt fiber strengthens anti-flaming polypropylene material.
Useful technique effect of the present invention is: the present invention with continuous basalt fiber Reinforced Polypropylene master batch and fire-retardant master granule in proportion blending form, can add simultaneously acrylic resin to regulate the content of basalt fibre and fire retardant, products obtained therefrom not only has good flame retardancy, good mechanical performance, and preparation technology is simple, with low cost, environmental friendliness, meet suitability for industrialized production and to requirements of green environmental protection, wide market application prospect is arranged.
Embodiment
The present invention is described in further detail below in conjunction with specific embodiment, and following embodiment only is used for explanation the present invention, does not limit the present invention.
Embodiment 1
The preparation of continuous basalt fiber Reinforced Polypropylene master batch:
Acrylic resin HJ4045 (melting index 45g/10min) with 45%, 4% polar monomer graftomer type Compatibilizer C A100(maleic anhydride inoculated polypropylene), after 1% thermo-stabilizer (Tyox B mixes by 1:1 with 4-hydroxyl octadecane anilide) mixes, adopt the dipping die head, continuous basalt fiber is pulled through the dipping die head, be prepared into continuous basalt fiber Reinforced Polypropylene master batch, the content of continuous basalt fiber is 50%.
The preparation of fire-retardant master granule:
15% polypropylene PP, 320 powder (melting index 37g/10min), 63% TDE, 21% stibium trioxide and 1% thermo-stabilizer (4-hydroxyl octadecane anilide mixes by 1:1 with triphenyl phosphite) are mixed, melt pelletization in Banbury mixer obtains required fire-retardant master granule.
Continuous basalt fiber strengthens the preparation of anti-flaming polypropylene material:
Continuous basalt fiber Reinforced Polypropylene master batch, fire-retardant master granule and acrylic resin K1011 are pressed 2:2:1 mix, make needed continuous basalt fiber and strengthen anti-flaming polypropylene material.In final matrix material, polypropylene content is 44%, polar monomer graftomer type compatibilizer content is 1.6%, continuous basalt fiber content is 20%, thermo-stabilizer content is 0.8%, TDE content is 25.2%, and fire retarding synergist stibium trioxide content is 8.4%, and the above percentage composition all is weight percentage.
Embodiment 2
The preparation of continuous basalt fiber Reinforced Polypropylene master batch:
With embodiment 1;
The preparation of fire-retardant master granule:
39% bimodal polyethylene FB2230,45% TDE, 15% stibium trioxide and 1% thermo-stabilizer (4-hydroxyl octadecane anilide mixes by 1:1 with triphenyl phosphite) are mixed, and melt pelletization in Banbury mixer obtains required fire-retardant master granule.
Continuous basalt fiber strengthens the preparation of fire-retardant nylon material:
Continuous basalt fiber Reinforced Polypropylene master batch is mixed by 1:1 with fire-retardant master granule, make needed continuous basalt fiber and strengthen anti-flaming polypropylene material.In final matrix material, polypropylene content is 22.5%, bimodal polyethylene content 19.5%, polar monomer graftomer type compatibilizer content is 2%, continuous basalt fiber content is 25%, and thermo-stabilizer content is 1%, and TDE content is 22.5%, fire retarding synergist stibium trioxide content is 7.5%, and the above percentage composition all is weight percentage.
Embodiment 3
The preparation of continuous basalt fiber Reinforced Polypropylene master batch:
With embodiment 1;
The preparation of fire-retardant master granule:
With embodiment 1;
Continuous basalt fiber strengthens the preparation of fire-retardant nylon material:
Continuous basalt fiber Reinforced Polypropylene master batch is mixed by 3:1 with fire-retardant master granule, make needed continuous basalt fiber and strengthen anti-flaming polypropylene material.In final matrix material, polypropylene content is 37.5%, polar monomer graftomer type compatibilizer content is 3%, continuous basalt fiber content is 37.5%, thermo-stabilizer content is 1%, TDE content is 15.75%, and fire retarding synergist stibium trioxide content is 5.25%, and the above percentage composition all is weight percentage.
Embodiment 4
The preparation of continuous basalt fiber Reinforced Polypropylene master batch:
Acrylic resin K7760 (melting index 60g/10min) with 54%, 5% polar monomer graftomer type Compatibilizer C A100(maleic anhydride inoculated polypropylene), after 1% thermo-stabilizer (triphenyl phosphite mixes by 3:1 with 4-hydroxyl octadecane anilide) mixes, adopt the dipping die head, continuous basalt fiber is pulled through the dipping die head, be prepared into continuous basalt fiber Reinforced Polypropylene master batch, the content of continuous basalt fiber is 40%.
The preparation of fire-retardant master granule:
With embodiment 2;
Continuous basalt fiber strengthens the preparation of fire-retardant nylon material:
Continuous basalt fiber Reinforced Polypropylene master batch is mixed by 3:1 with fire-retardant master granule, make needed continuous basalt fiber and strengthen anti-flaming polypropylene material.In final matrix material, polypropylene content is 40.5%, bimodal polyethylene content 9.75%, polar monomer graftomer type compatibilizer content is 3.75%, continuous basalt fiber content is 30%, and thermo-stabilizer content is 1%, and TDE content is 11.25%, fire retarding synergist stibium trioxide content is 3.75%, and the above percentage composition all is weight percentage.
Embodiment 5
The preparation of continuous basalt fiber Reinforced Polypropylene master batch:
With embodiment 4;
The preparation of fire-retardant master granule:
27% linear low density polyethylene M500026 (melting index 40g/10min), 54% TDE, 18% stibium trioxide and 1% thermo-stabilizer (4-hydroxyl octadecane anilide mixes by 1:1 with triphenyl phosphite) are mixed, melt pelletization in Banbury mixer obtains required fire-retardant master granule.
Continuous basalt fiber strengthens the preparation of fire-retardant nylon material:
Continuous basalt fiber Reinforced Polypropylene master batch is mixed by 2:1 with fire-retardant master granule, make needed continuous basalt fiber and strengthen anti-flaming polypropylene material.In final matrix material, polypropylene content is 36%, polymerized ethylene content 9%, polar monomer graftomer type compatibilizer content is 3.3%, continuous basalt fiber content is 26.7%, and thermo-stabilizer content is 1%, and TDE content is 18%, fire retarding synergist stibium trioxide content is 6%, and the above percentage composition all is weight percentage.
Embodiment 6
The preparation of continuous basalt fiber Reinforced Polypropylene master batch:
Acrylic resin HJ4045 (melting index 45g/10min) with 40%, 2% polar monomer graftomer type Compatibilizer C A100(maleic anhydride inoculated polypropylene), 1.5% thermo-stabilizer (Tyox B mixes by 1:1 with 4-hydroxyl octadecane anilide) and 1.5% mix lubricant evenly after, adopt the dipping die head, 55% continuous basalt fiber is pulled through the dipping die head, be prepared into continuous basalt fiber Reinforced Polypropylene master batch, the content of continuous basalt fiber is 55%.
The preparation of fire-retardant master granule:
35% polypropylene PP, 320 powder (melting index 37g/10min), 50% TDE, 14% stibium trioxide, 0.5% thermo-stabilizer (4-hydroxyl octadecane anilide mixes by 1:1 with triphenyl phosphite) and 0.5% mix lubricant is even, melt pelletization in Banbury mixer obtains required fire-retardant master granule.
Continuous basalt fiber strengthens the preparation of anti-flaming polypropylene material:
Continuous basalt fiber Reinforced Polypropylene master batch, fire-retardant master granule and acrylic resin K1011 are pressed 2:2:1 mix, make needed continuous basalt fiber and strengthen anti-flaming polypropylene material.In final matrix material, polypropylene content is 50%, polar monomer graftomer type compatibilizer content is 0.8%, continuous basalt fiber content is 22%, thermo-stabilizer content is 0.8%, TDE content is 20%, and fire retarding synergist stibium trioxide content is 5.6%, and the above percentage composition all is weight percentage.
The Performance Detection data of the various embodiments described above gained material are as shown in table 1, wherein the mechanical test project is carried out according to iso standard, be respectively: tensile strength ISO 527-2, flexural strength and modulus in flexure ISO 178, notched Izod impact strength ISO 180/1A, flame retardant properties UL94 standard, and used thermo-stabilizer and lubricant are this area product commonly used in the various embodiments described above.
NM working method and processing condition etc. are technology contents well-known to those skilled in the art in the various embodiments described above, repeat no more among the present invention.
Table 1
Claims (8)
1. a continuous basalt fiber strengthens anti-flaming polypropylene material, it is characterized in that: mainly formed by 40 ~ 75wt.% continuous basalt fiber Reinforced Polypropylene master batch and 25 ~ 40% fire-retardant master granule blending; Wherein said continuous basalt fiber Reinforced Polypropylene master batch mainly is made up of 40 ~ 55wt.% continuous basalt fiber, 40 ~ 54 wt.% acrylic resins and 2 ~ 5 wt.% polar monomer graftomer type compatilizers; Described fire-retardant master granule mainly is made up of 15 ~ 39 wt.% polyolefin resines, 45 ~ 63wt.% fire retardant and 14 ~ 21 wt.% fire retarding synergists; Wherein said fire retardant is at least a in TDE, decabromodiphenyl oxide and the decabromodiphenyl, and described fire retarding synergist is stibium trioxide.
2. continuous basalt fiber according to claim 1 strengthens anti-flaming polypropylene material, it is characterized in that: but described continuous basalt fiber strengthens the acrylic resin that anti-flaming polypropylene material also comprises regulated quantity.
3. continuous basalt fiber according to claim 1 strengthens anti-flaming polypropylene material, and it is characterized in that: described continuous basalt fiber Reinforced Polypropylene master batch and described fire-retardant master granule all also comprise the thermo-stabilizer of dosage and the lubricant of dosage.
4. continuous basalt fiber according to claim 1 strengthens anti-flaming polypropylene material, it is characterized in that: the polyolefin resin in the described fire-retardant master granule in melting index under the 2.16kg/230 ℃ of test condition greater than the polypropylene of 20g/10min, melting index presents at least a in the polyethylene that is no less than two peaks greater than the polyethylene of 20g/10min and molecular weight distribution curve under 1.90 kg/230 ℃ test condition.
5. continuous basalt fiber according to claim 1 strengthens anti-flaming polypropylene material, and it is characterized in that: described fire retardant is TDE.
6. continuous basalt fiber according to claim 1 strengthens anti-flaming polypropylene material, it is characterized in that: the polymkeric substance in the described polar monomer graftomer type compatilizer is at least a in polyethylene, polypropylene, ethylene-butene copolymer and the ethylene-octene copolymer, and described polar monomer is at least a in maleic anhydride, vinylformic acid and the acrylate.
7. continuous basalt fiber according to claim 6 strengthens anti-flaming polypropylene material, and it is characterized in that: described polar monomer graftomer type compatilizer is maleic anhydride inoculated polypropylene.
8. strengthen the preparation method of anti-flaming polypropylene material according to the described continuous basalt fiber of arbitrary claim in the claim 1 to 7, it is characterized in that: may further comprise the steps:
(1) preparation of continuous basalt fiber Reinforced Polypropylene master batch: the lubricant of the thermo-stabilizer of 40 ~ 54% acrylic resins, 2 ~ 5wt.% polar monomer graftomer type compatilizer, dosage and the dosage spout from twin screw extruder is added, carry out abundant fusion and mix, after then 40 ~ 55wt.% continuous basalt fiber being pulled out from die head especially used, successively through supercooled water but, the dicing machine granulation, obtaining length is the continuous basalt fiber Reinforced Polypropylene master batch of 5 ~ 12mm;
(2) preparation of fire-retardant master granule: the lubricant of the thermo-stabilizer of 15 ~ 39 wt.% polyolefin resines, 45 ~ 63 wt.% fire retardants, 14 ~ 21 wt.% fire retarding synergists, dosage and dosage is added in the banburying chamber of Banbury mixer and mix and melt pelletization, get fire-retardant master granule;
(3) obtain continuous basalt fiber after the acrylic resin of obtained flame-retardant master batch, regulated quantity in gained continuous basalt fiber Reinforced Polypropylene master batch, (2) in (1) is mixed in proportion and strengthen anti-flaming polypropylene material, wherein continuous basalt fiber Reinforced Polypropylene master batch accounts for 40 ~ 75wt.% that continuous basalt fiber strengthens fire-retardant nylon material, fire-retardant master granule accounts for 25 ~ 40wt.% that continuous basalt fiber strengthens fire-retardant nylon material, and continuous basalt fiber accounts for 20 ~ 37.5wt.% that continuous basalt fiber strengthens anti-flaming polypropylene material.
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| 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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