CN105086161A - Novel halogen-free flame retardant composite material and preparation method thereof - Google Patents
Novel halogen-free flame retardant composite material and preparation method thereof Download PDFInfo
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- CN105086161A CN105086161A CN201510547999.6A CN201510547999A CN105086161A CN 105086161 A CN105086161 A CN 105086161A CN 201510547999 A CN201510547999 A CN 201510547999A CN 105086161 A CN105086161 A CN 105086161A
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention provides a novel halogen-free flame retardant composite material. The novel halogen-free flame retardant composite material comprises the following components in percentage by weight: 28% to 64.5% of polypropylene, 10% to 20% of thermoplastic polyurethane elastomer, 5% to 10% of bulking agent, 15% to 25% of halogen-free flame retardant agent, 5% to 15% of flame retardant synergist, and 0.5% to 2% of coupling agent, wherein the total percentage of the components by weight is 100%. The invention also aims at providing a preparation method of the novel halogen-free flame retardant composite material. The novel halogen-free flame retardant composite material has the advantages that the preparation technology is simple, the mechanical property is good, the high temperature-resistant property and flame-retardant property are realized, the efficiency is high, the clean and environment-friendly effects are realized, and the novel halogen-free flame retardant composite material can be widely applied to the fields of automobiles, household parts and accessories, wires and cables, and the like.
Description
Technical field
The present invention relates to a kind of novel halogen-free flame-retardant matrix material and preparation method thereof, particularly relate to a kind of polypropylene/Polyurethane Thermoplastic Elastomer halogen-free flame-retardant composite material and preparation method thereof.
Background technology
As one of five large general-purpose plastics, the comprehensive mechanical property of polypropylene (PP) is excellent, there is good dielectric properties and high-frequency insulation and not by humidity effect, in addition, PP also has higher thermotolerance, chemical property is good, absorbs water hardly, does not react with most pharmaceutical chemicals.Because its excellent over-all properties, PP has become indispensable base mateiral in our daily life, particularly in household electrical appliance, plastic pipe, high material and electric wire and cable material field thoroughly.But PP also has shortcoming, its low impelling strength and inflammableness seem particularly fatal.So PP is toughness reinforcing and PP is fire-retardant always is the focus that academic and Industrial materials are studied and difficult point.
For improving the toughness of PP, intermingling material and the goods of the multiple elastomericss such as ethylene-octene copolymer (POE), styrene-butadiene-styrene block copolymer (SBS), terpolymer EP rubber (EPDM), natural rubber (NR) and isoprene-isobutylene rubber (IIR) and PP are are researched and developed.These elasticity physical efficiencys improve the toughness of PP effectively, but these constituent materialss all embody nonpolar feature, limit the application in some occasion of PP and these PP matrix materials, especially require to have certain polarity and hydrophilic occasion, as print coating.
Therefore, develop flame retardant effect good, mechanical property is excellent, and Novel polypropylene material applied widely has important practical significance.
Summary of the invention
The object of the invention is to avoid weak point of the prior art and a kind of good mechanical properties is provided, the novel halogen-free flame-retardant matrix material of efficient, the clean environmental protection of flame retardant properties.
Another object of the present invention is to the preparation method that the simple novel halogen-free flame-retardant matrix material of a kind of technique is provided.
The first object of the present invention can reach by taking following technical scheme:
A kind of novel halogen-free flame-retardant matrix material, is characterized in that: described matrix material comprises following composition by weight percentage: polypropylene (PP): 28-64.5%; Polyurethane Thermoplastic Elastomer (TPU): 10-20%; Expanding material: 5-10%; Halogen-free flame retardants: 15-25%; Fire retarding synergist: 5-15%; Coupling agent: 0.5-2%; The weight percent sum of mentioned component is 100%.
Preferably, described polypropylene is copolymerized type propene polymer.
Preferably, the described copolymerized type propene polymer 3015 model copolymerized type propene polymers of selecting Yongjia, Taiwan chemical industry limited-liability company to produce.
Preferably, described Polyurethane Thermoplastic Elastomer is polyester type Polyurethane Thermoplastic Elastomer.
Preferably, the BF85 model polyester type TPU that described polyester type Polyurethane Thermoplastic Elastomer selects Lubrizol Corp. of the U.S. to produce, its limiting oxygen index(LOI) is 26-28.
Preferably, described expanding material is EDPM-g-MAH or POE-g-MAH.
Wherein, EDPM-g-MAH is the grafts of terpolymer EP rubber (EDPM) and maleic anhydride (MAH); POE-g-MAH is the grafts of polyolefin elastomer (POE) and maleic anhydride (MAH).
Preferably, described expanding material is POE-g-MAH.
Preferably, described halogen-free flame retardants is hypo-aluminum orthophosphate or aluminum diethylphosphinate.
Preferably, described halogen-free flame retardants is hypo-aluminum orthophosphate.
Preferably, described fire retarding synergist is the compound flame retardant of melamine cyanurate (MCA) and zinc borate.
Preferably, in described compound flame retardant, the mass ratio of melamine cyanurate and zinc borate is 1:1; The mass ratio of described hypo-aluminum orthophosphate and described compound flame retardant is 2:1.
Preferably, described coupling agent is silane coupling agent.
Preferably, described silane coupling agent selects silane coupling agent KH560.
The second object of the present invention can reach by taking following technical scheme:
A preparation method for novel halogen-free flame-retardant matrix material, is characterized in that, comprises the steps:
1) according to formulation ratio, all raw materials are mixed, stir, obtain mixture;
2) send the mixture stirred to forcing machine, mixture reacts in an extruder, and the reaction times is 3-5min, temperature of reaction 180-190 DEG C, obtains the compound being in molten state;
3) after the compound being in molten state being squeezed into strip outflow, first entering cooling process under water, then carry out pelletizing operation, obtain polypropylene/thermoplastic polyurethane elastomer composite material pellet.
Compared to existing technology, beneficial effect of the present invention is:
(1) because TPU had both had the snappiness of rubber, have again the processibility of thermoplastics, it has excellent elasticity, wear resistance, oil-proofness, ageing-resistant and stronger polarity etc.TPU and PP is mixed with out PP/TPU matrix material by the present invention, obviously can improve the low shortcoming of PP impelling strength, can also increase wear resistance and the oil-proofness of PP simultaneously.
(2) PP/TPU composite material preparation process is simple, and good mechanical properties is high temperature resistant, and flame retardant properties is efficient, clean environmental protection.The introduction of TPU polarity expands the Application Areas of PP, can be widely used in the field such as automobile and household electrical appliances spare and accessory parts, electric wire.
(3) the present invention selects copoly type PP, and copoly type PP has better shock strength and lower temperature resistance than homopolymerization PP.
(4) limiting oxygen index(LOI) (LOI) of polyester type TPU of the present invention is 26-28, therefore the flame retardant resistance of the compound of TPU and PP to PP improves.After adding efficient fire retardant, PP/TPU matrix material is applicable to high-grade flame retardant resistance field, has wide range of applications.
(5) polyolefin backbone in expanding material of the present invention can combine with PP, maleic anhydride (MAH) can combine with the ester bond reacting phase in TPU molecular chain, therefore expanding material of the present invention can improve PP and TPU consistency significantly, thus improves the mechanical strength of PP/TPU.Meanwhile, the polar link of MAH and halogen-free flame retardants and MCA polar link cohesive force good, thus promote fire-retardant dispersion in the alloy and improve the cohesive force of fire retardant and resin.
(6) the present invention selects hypo-aluminum orthophosphate or aluminum diethylphosphinate to be halogen-free flame retardants, and the decomposition temperature of hypo-aluminum orthophosphate, aluminum diethylphosphinate is higher than 300 DEG C, higher than conventional phosphor nitrogen combustion inhibitor decomposition temperature.Therefore fire-retardant PP/TPU matrix material prepared by the present invention has better surface and higher heat resistance.
(7) the present invention selects the compound flame retardant of MCA and zinc borate to be fire retarding synergist, adding of MCA can as source of the gas, and zinc borate can improve carbon-coating quality, play cooperative flame retardant effect with aluminum phosphate as acid source and carbon source, reduce the cost of overall flame agent simultaneously.
(8) the present invention selects silane coupling agent, and silane coupling agent can improve the cohesive force between resin and fire retardant, improves the dispersion of fire retardant, improves the mechanical property of matrix material.
Embodiment
Below, in conjunction with embodiment, the present invention is described further:
Embodiment 1
A preparation method for novel halogen-free flame-retardant matrix material, comprises the following steps:
(1) according to weight percent meter, by 54%PP, 10%TPU, 20% hypo-aluminum orthophosphate, 10% fire retarding synergist, after 5%EDPM-g-MAH and 1% coupling agent mixing and stirring, obtains compound; Wherein, described fire retarding synergist is the compound flame retardant of MCA and zinc borate, and wherein, the mass ratio of MCA and zinc borate is 1:1; KH560 silane coupling agent selected by described coupling agent.
(2) mixture that will stir through step (1) sends into forcing machine, and the compound reaction times is in an extruder 3-5min, and temperature of reaction is 180-190 DEG C, obtains the mixture being in molten state;
(3) be in mixture under molten state to be squeezed into strip through forcing machine and to flow out, after cooling process under water, carry out pelletizing operation, obtained PP/TPU matrix material pellet.Product performance refer to table 1.
Embodiment 2
A preparation method for novel halogen-free flame-retardant matrix material, comprises the following steps:
(1) according to weight percent meter, by 44%PP, 20%TPU, 20% hypo-aluminum orthophosphate, 10% fire retarding synergist, after 5%EDPM-g-MAH and 1% coupling agent mixing and stirring, obtains compound; Wherein, described fire retarding synergist is MCA and zinc borate mass ratio is the compound flame retardant of 1:1; KH560 silane coupling agent selected by described coupling agent.
(2) mixture that will stir through step (1) sends into forcing machine, and the mixture reaction times is in an extruder 3-5min, and temperature of reaction is 180-190 DEG C, obtains the mixture being in molten state;
(3) be in mixture under molten state to be squeezed into strip through forcing machine and to flow out, after cooling process under water, carry out pelletizing operation, obtained PP/TPU matrix material pellet.Product performance refer to table 1.
Embodiment 3
A preparation method for novel halogen-free flame-retardant matrix material, comprises the following steps:
According to weight percent meter, by 54%PP, 10%TPU, 20% hypo-aluminum orthophosphate, 10% fire retarding synergist, 5%POE-g-MAH, after 1% coupling agent mixing and stirring, obtains mixture.Wherein, described fire retarding synergist is MCA and zinc borate mass ratio is the compound flame retardant of 1:1; KH560 silane coupling agent selected by described coupling agent.
Other are identical with embodiment 1.Product property refers to table 1.
Embodiment 4
A preparation method for novel halogen-free flame-retardant matrix material, comprises the following steps:
According to weight percent meter, by 54%PP, 10%TPU, 15% hypo-aluminum orthophosphate, 15% fire retarding synergist, 5%EPDM-g-MAH, after 1% coupling agent mixing and stirring, obtains mixture.Wherein, described fire retarding synergist is MCA and zinc borate mass ratio is the compound flame retardant of 1:1; KH560 silane coupling agent selected by described coupling agent.
Other are identical with embodiment 1.Product property refers to table 1.
Table 1 particular product performance parameters experimental result contrast table
As can be seen from Table 1, PP/TPU halogen-free flame-retardant composite material good mechanical properties provided by the invention, shock-resistant ability is strong, good toughness; Limiting oxygen index(LOI) is all greater than 28, and fire-protection rating UL-94 reaches V-0, V-1 grade, belongs to nonflammable material, high temperature resistant, and flame retardant properties is good.PP/TPU halogen-free flame-retardant composite material provided by the invention has wide range of applications, and is applicable to the field such as automobile and household electrical appliances spare and accessory parts, electric wire.
Other embodiments: the additives such as other appropriate catalysts, antioxidants can also be added in formula of the present invention.
To one skilled in the art, according to technical scheme described above and design, other various corresponding change and deformation can be made, and all these change and deformation all should belong within the protection domain of the claims in the present invention.
Claims (10)
1. a novel halogen-free flame-retardant matrix material, is characterized in that: described matrix material comprises following composition by weight percentage:
Polypropylene: 28-64.5%;
Polyurethane Thermoplastic Elastomer: 10-20%;
Expanding material: 5-10%;
Halogen-free flame retardants: 15-25%;
Fire retarding synergist: 5-15%;
Coupling agent: 0.5-2%;
The weight percent sum of mentioned component is 100%.
2. novel halogen-free flame-retardant matrix material according to claim 1, is characterized in that: described polypropylene is copolymerized type propene polymer.
3. novel halogen-free flame-retardant matrix material according to claim 1, is characterized in that: described Polyurethane Thermoplastic Elastomer is polyester type Polyurethane Thermoplastic Elastomer.
4. novel halogen-free flame-retardant matrix material according to claim 3, is characterized in that: the limiting oxygen index(LOI) of described polyester type Polyurethane Thermoplastic Elastomer is 26-28.
5. novel halogen-free flame-retardant matrix material according to claim 1, is characterized in that: described expanding material is EDPM-g-MAH or POE-g-MAH.
6. novel halogen-free flame-retardant matrix material according to claim 1, is characterized in that: described halogen-free flame retardants is hypo-aluminum orthophosphate or aluminum diethylphosphinate.
7. novel halogen-free flame-retardant matrix material according to claim 6, is characterized in that: described fire retarding synergist is the compound flame retardant of melamine cyanurate and zinc borate.
8. novel halogen-free flame-retardant matrix material according to claim 7, is characterized in that: the mass ratio of described melamine cyanurate and zinc borate is 1:1, and the mass ratio of described hypo-aluminum orthophosphate and described compound flame retardant is 2:1.
9. novel halogen-free flame-retardant matrix material according to claim 1, is characterized in that: described coupling agent is silane coupling agent.
10., according to a preparation method for the novel halogen-free flame-retardant matrix material in claim 1-9 described in any one, it is characterized in that, comprise the steps:
1) according to formulation ratio, all raw materials are mixed, stir, obtain mixture;
2) send the mixture stirred to forcing machine, mixture reacts in an extruder, and the reaction times is 3-5min, temperature of reaction 180-190 DEG C, obtains the compound being in molten state;
3) after the compound being in molten state being squeezed into strip outflow, first entering cooling process under water, then carry out pelletizing operation, obtain polypropylene/thermoplastic polyurethane elastomer composite material pellet.
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| CN105602071A (en) * | 2016-03-21 | 2016-05-25 | 江苏德威新材料股份有限公司 | High-temperature-irradiation-resistant halogen-free flame-retardant automobile wire material and preparation method thereof |
| CN106046751A (en) * | 2016-07-05 | 2016-10-26 | 安徽吉安特种线缆制造有限公司 | Anti-ultraviolet cracking-resistant cable material for locomotive |
| CN108699306A (en) * | 2016-03-14 | 2018-10-23 | 博里利斯股份公司 | Polypropene composition including fire retardant |
| WO2018192163A1 (en) * | 2017-04-20 | 2018-10-25 | 贵州省材料产业技术研究院 | Dynamic vulcanisation flame retardant tpv composite material and preparation method therefor |
| CN109593267A (en) * | 2018-10-19 | 2019-04-09 | 宁波帅特龙集团有限公司 | A kind of handle of automobile roof and preparation method thereof |
| CN109942927A (en) * | 2017-12-21 | 2019-06-28 | 陈正林 | A kind of high molecular abrasion-proof band can increase wearability |
| CN111138830A (en) * | 2018-11-05 | 2020-05-12 | 苏州市朗腾工贸有限公司 | Flame-retardant elastomer automobile sheath material and processing technology |
| CN111925645A (en) * | 2020-08-12 | 2020-11-13 | 九焱新材料(深圳)有限公司 | Halogen-free flame-retardant thermoplastic polyurethane elastomer composite material and preparation method thereof |
| CN113881216A (en) * | 2021-11-24 | 2022-01-04 | 国网河南省电力公司镇平县供电公司 | Wear-resistant flame-retardant modified polyurethane cable material and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108699306A (en) * | 2016-03-14 | 2018-10-23 | 博里利斯股份公司 | Polypropene composition including fire retardant |
| CN105602071A (en) * | 2016-03-21 | 2016-05-25 | 江苏德威新材料股份有限公司 | High-temperature-irradiation-resistant halogen-free flame-retardant automobile wire material and preparation method thereof |
| CN105602071B (en) * | 2016-03-21 | 2018-06-15 | 江苏德威新材料股份有限公司 | High temperature resistant irradiation halogen-free flameproof automobile strands and preparation method thereof |
| CN106046751A (en) * | 2016-07-05 | 2016-10-26 | 安徽吉安特种线缆制造有限公司 | Anti-ultraviolet cracking-resistant cable material for locomotive |
| WO2018192163A1 (en) * | 2017-04-20 | 2018-10-25 | 贵州省材料产业技术研究院 | Dynamic vulcanisation flame retardant tpv composite material and preparation method therefor |
| CN109942927A (en) * | 2017-12-21 | 2019-06-28 | 陈正林 | A kind of high molecular abrasion-proof band can increase wearability |
| CN109593267A (en) * | 2018-10-19 | 2019-04-09 | 宁波帅特龙集团有限公司 | A kind of handle of automobile roof and preparation method thereof |
| CN111138830A (en) * | 2018-11-05 | 2020-05-12 | 苏州市朗腾工贸有限公司 | Flame-retardant elastomer automobile sheath material and processing technology |
| CN111925645A (en) * | 2020-08-12 | 2020-11-13 | 九焱新材料(深圳)有限公司 | Halogen-free flame-retardant thermoplastic polyurethane elastomer composite material and preparation method thereof |
| CN113881216A (en) * | 2021-11-24 | 2022-01-04 | 国网河南省电力公司镇平县供电公司 | Wear-resistant flame-retardant modified polyurethane cable material and preparation method thereof |
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