CN111117055B - High-flame-retardant low-gloss dynamic vulcanization thermoplastic elastomer material and continuous preparation method thereof - Google Patents
High-flame-retardant low-gloss dynamic vulcanization thermoplastic elastomer material and continuous preparation method thereof Download PDFInfo
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- 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
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Abstract
The invention discloses a high-flame-retardance low-gloss dynamic vulcanization thermoplastic elastomer material and a continuous preparation method thereof. The thermoplastic elastomer material can improve the impact resistance in the presence of a flame retardant and has excellent flame retardant performance, the V0 level can still be achieved under the condition of 0.8mm thickness, the gloss of the material is reduced by using special lipophilic silicon dioxide and polyethylene wax, and the gloss can be obviously reduced. The production process of the dynamic vulcanization thermoplastic elastomer has the advantages of low energy consumption and greatly reduced production cost, and is very suitable for large-scale process production.
Description
Technical Field
The invention relates to a high-flame-retardant low-gloss dynamic vulcanized thermoplastic elastomer and a continuous preparation method thereof, belonging to the field of synthesis and processing of high polymer materials.
Background
Owing to the high elasticity and good mechanical properties exhibited by chemical crosslinking, rubber products are widely applied to various industries at present, but the drastic increase of the dosage also leads people to find the recovery and decomposition of the materials and the difficulty thereof, which has very high risk in the modern with high environmental protection requirement. Such as waste tires and vehicle sealing strips, etc., can cause great damage to the environment.
Dynamically vulcanized thermoplastic elastomer (TPV) refers to a stable two-phase dispersion system formed by melt blending rubber and thermoplastic resin under the action of high-temperature shearing, vulcanizing the rubber in situ by using a crosslinking agent and dispersing the vulcanized rubber in the resin. TPV has thermoplasticity of plastics, can be repeatedly processed and used, is convenient to recycle, has high elasticity and mechanical property of the traditional rubber, and eliminates the embarrassment that the TPV cannot be recycled. As a novel green polymer material, TPV (thermoplastic vulcanizate) is well applied to a plurality of fields such as automobiles, electronics and the like, has very high economic value and social benefit, and becomes the polymer material which is developed most rapidly in recent years.
At present, the rubber applied to the preparation of TPV mainly comprises ethylene propylene rubber, butyl rubber, natural rubber, styrene-butadiene rubber and the like, and the thermoplastic resin mainly comprises polypropylene, polyethylene, polyamide, polystyrene and the like. The rubber is usually a blocky material, and the rubber is difficult to mix with thermoplastic resin due to high viscosity, so that a special crushing and banburying device is required to be arranged at the front end of TPV preparation, the blocky rubber is crushed into rubber powder with the diameter within 1mm, and the rubber powder is fully mixed with the thermoplastic resin through banburying to be put into a subsequent dynamic crosslinking process, so that the conventional TPV production process is complicated and complex, and the cost is high.
New energy automobiles, particularly electric automobiles, develop rapidly in recent years, but with the occurrence of spontaneous combustion accidents of a plurality of electric automobiles, the flame retardant property of automobile materials is more limited and required, for example, materials of parts such as door panels, instrument panels, decorative columns and the like need to meet the rigidity requirement and have good impact property, and cannot crack or form sharp fragments when resisting external force impact, but the impact property of the materials can be greatly reduced due to the addition of flame retardants at present, and most of automobile interior materials are difficult to meet the flame retardant requirement at present. In addition, in consideration of driving safety, materials in areas where the driver looks at need low gloss to avoid unsafe factors such as dazzling, but traditional interior materials are high in gloss and have great potential safety hazards.
In conclusion, it is urgently needed to develop a novel dynamically vulcanized thermoplastic elastomer material which has high flame retardant property and good impact property, can solve the potential safety hazard of high glossiness, can overcome the disadvantage of complex preparation process of the conventional TPV, can realize simple and continuous production, and meets the requirement of large-scale production.
Disclosure of Invention
The invention aims to provide a high-flame-retardance low-gloss dynamically vulcanized thermoplastic elastomer which has high flame retardance and good impact property and achieves ultralow gloss.
The invention also aims to provide a continuous preparation method of the dynamically vulcanized thermoplastic elastomer material, which overcomes the disadvantage of complicated preparation process of the conventional TPV, can realize continuous production and is suitable for industrial mass production.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a high flame-retardant low-gloss dynamically vulcanized thermoplastic elastomer material is characterized in that: the melt flow index is 230 ℃, the test value under 2.16KG is 2-40 g/10min, the flame retardant grade is V0 (the thickness of a sample strip is 0.8 mm), and the flame retardant grade comprises the following raw materials in parts by mass or is prepared from the following raw materials in parts by mass:
100 parts of ethylene-butylene elastomer;
30-75 parts of polypropylene, preferably 35-70 parts;
0.5-8 parts of cross-linking agent, preferably 1-5 parts;
0.5-12 parts of lipophilic silicon dioxide, preferably 1-10 parts;
0.5-8 parts of polyethylene wax, preferably 1-5 parts;
0.05-4 parts of auxiliary crosslinking agent, preferably 0.1-2 parts;
10-55 parts of halogen flame retardant, preferably 15-50 parts;
3-25 parts of flame retardant auxiliary agent, preferably 5-20 parts;
0.5-12 parts of anti-dripping agent, preferably 1-10 parts;
0.5-7 parts of lubricant, preferably 1-5 parts;
0.5-5 parts of antioxidant, preferably 1-3 parts.
Furthermore, the content of the butylene in the ethylene-butylene elastomer is 20-50%, the melt flow index is 190 ℃, the test value under 2.16KG is 0.1-40 g/10min, the glass transition temperature is lower than minus 50 ℃, the crystallization temperature is 30-50 ℃, and the content of the butylene in the polymer is 35-40%.
Further, the median particle diameter D50 of the lipophilic silicon dioxide is 1-10 μm, siloxane groups are grafted on the surface, and the specific molecular structure is as follows:
wherein R is 1 Is one of hydrogen atom and methyl, R 2 Is one of methoxy, ethoxy, isopropoxy and isobutoxyThe graft content of siloxane groups is 1 to 20%, further optimized to 1 to 5%.
Polyolefin elastomers (POE) are a kind of ethylene and alpha-olefin copolymer, the introduction of alpha-olefin destroys the original polyethylene crystalline phase structure and forms connecting points among molecular chains, so that the material is subjected to the action of impact energy dispersion when impacted, and the material is endowed with better impact resistance and toughness and has good mechanical properties and processability. POE is mainly classified into two major classes, ethylene-butene copolymer and ethylene-octene copolymer, wherein ethylene-butene copolymer has better low temperature impact resistance and toughening effect than ethylene-octene copolymer, which is related to butene having shorter molecular chain length.
More importantly, the glass transition temperature of the traditional ethylene-butene copolymer is higher, usually higher than-50 ℃, so that the toughening effect on the material is limited.
In the preferred embodiment of the invention, the selected ethylene-butylene copolymer material has the glass transition temperature lower than-50 ℃, high butylene content and better toughening effect, and can endow the material with better mechanical properties.
Compared with ethylene propylene diene monomer EPDM, POE has many advantages: (1) The EPDM rubber is easy to add and use, and a crushing machine for EPDM is not required to be equipped; (2) The melt has good fluidity and convenient processing, and the EPDM mixing process is not required; (3) The molecular weight distribution is narrow, and the rubber has better weather resistance and aging resistance than EPDM. Therefore, the POE is used for replacing the EPDM to prepare the dynamic vulcanization thermoplastic elastomer, the original complicated production process can be simplified, and better impact resistance of the elastomer can be achieved.
According to different application requirements, the flame retardant property of the material has different requirements, and the flame retardant property evaluation method also has various test standards. UL-94 is the most widely used plastic material flame retardant performance test method, used for evaluating the ability of the material to extinguish after being ignited, and is divided into three grades of V0, V1 and V2, the V0 flame retardant grade is the highest, and the evaluation is mainly carried out in the aspects of testing the thickness of a sample strip, the burning speed, the burning time, the anti-dripping ability and whether the dripping beads are burnt. The thickness of the test sample strip has the largest influence on the flame retardant property, and the thinner the sample strip is, the better the combustible property is and the larger the flame retardant difficulty is. At present, the spline with the thickness of 0.8mm is the thinnest spline which is common at present, so the 0.8mmV0 grade is the requirement of the highest-grade flame retardance at present. In V0 flame retardance, the problem that the absorbent cotton cannot be ignited after the material drips is mainly solved by avoiding the dripping of the material during combustion and inhibiting the burning of the dripping matters.
The achievement of low gloss of a material is in fact strongly related to the reflection and scattering of light. The addition of the ethylene-butylene copolymer and the elastomer in the material can reduce the reflectivity of the material, thereby effectively reducing the glossiness of the material. More importantly, the reduction of the gloss is closely related to the scattering of light, and the invention unexpectedly finds that the lipophilic silicon dioxide has a very good effect of reducing the gloss. On one hand, the surface of the traditional silicon dioxide is provided with polar hydroxysilane groups, the compatibility with polyolefin materials is poor, the compatibility of oleophylically modified silicon dioxide particles and polyolefin is improved, a scattering effect can be achieved on the surface of the materials, and the glossiness is reduced, on the other hand, the particle size of the silicon dioxide can also influence the scattering of light, and the 1-10 micron silicon dioxide can well scatter light, so that the glossiness of the materials is reduced.
Preferably, the polypropylene is a mixture of ethylene-propylene block copolymer polypropylene and homo-polypropylene, the melt flow index is 230 ℃, the test value under 2.16KG is 20-150 g/10min, and the ethylene content is 10-40%.
Preferably, the polyethylene wax has a weight average molecular weight of 2000-10000 Dalton, a melt flow index of 230 ℃ and a test value of 300-1000 g/10min under 2.16KG.
The polypropylene can be classified into ethylene-propylene random copolymer polypropylene, ethylene-propylene block copolymer polypropylene and homo-polypropylene according to molecular structure. The ethylene-propylene random copolymerization polypropylene has a good transparent effect because ethylene and propylene repeating units are randomly arranged, and the polypropylene crystallization can be effectively inhibited, but the material has poor rigidity and is difficult to be applied to vehicle materials. The homopolymerized polypropylene is formed by regular arrangement of propylene repeating units, has high crystallinity and strong rigidity, but has poor toughness and brittle material quality, and is difficult to independently apply to vehicle materials. The ethylene-propylene block copolymer polypropylene has the advantages that ethylene and propylene repeating units are regularly arranged in a block mode, so that the integral crystallization of the polypropylene can be partially inhibited, the rigidity of the material can be ensured, and the integral material has good rigidity and impact resistance. In polypropylene, the low ethylene content is poor impact resistance of the material, the excessively high material rigidity is low, and the overall performance of the material is balanced when the ethylene content is 10-40%. Based on the use environment of the automotive material, the polypropylene material is required to have excellent rigidity while ensuring good impact resistance, so that the block copolymer and the homo-polypropylene are used in a compounding manner, the advantages of the block copolymer and the homo-polypropylene are combined, and the excellent mechanical property is embodied.
The polyethylene wax has small molecular weight and high fluidity, and has the effects of increasing the ethylene content of the material, reducing the reflectivity of the material and further reducing the glossiness of the material, enhancing the compatibility of silicon dioxide particles and promoting the dispersion of the silicon dioxide and the bonding force with matrix polyolefin resin by utilizing the high fluidity of the polyethylene wax.
Preferably, the cross-linking agent is one or a mixture of more than two of benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butylperoxycumyl, 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane, azobisisobutyronitrile and azobisisoheptonitrile.
Preferably, the auxiliary crosslinking agent is one or a mixture of more than two of glycidyl methacrylate, N' -m-phenylene bismaleimide, triallyl isocyanurate, trimethylolpropane triacrylate, stannous chloride and stilbene.
Preferably, the halogen flame retardant system (also called composite flame retardant) comprises a halogen flame retardant and a flame retardant auxiliary agent, and the ratio of the halogen flame retardant to the flame retardant auxiliary agent is 5:1 to 2:1, the halogen flame retardant has the following structural formula:
wherein R is 1 is-SO 2 -, -CO-R 2 Is one of oxygen atom, sulfur atom and selenium atom, R 3 Is one of fluorine atom, chlorine atom and bromine atom, the flame retardant auxiliary agent is one of bismuth trioxide and arsenic trioxide,
preferably, the anti-dripping agent is one of zinc borate, silver borate, copper borate and nickel borate.
Preferably, the lubricant is one or a mixture of more than two of ethylene bis-fatty acid amide and pentaerythritol stearate, and the antioxidant is one or more of hindered phenol antioxidant, thiodipropionic acid bis-ester antioxidant and phosphite antioxidant.
According to the second aspect of the present invention, a continuous preparation method of the above-mentioned high flame retardant low gloss dynamically vulcanized thermoplastic elastomer material is provided, which comprises the steps of mixing uniformly ethylene-butylene elastomer, lipophilic silica, polypropylene, polyethylene wax, anti-dripping agent, lubricant and antioxidant, feeding from a feeding port of a feeding section, mixing uniformly crosslinking agent and auxiliary crosslinking agent, feeding at a first feeding port of a melting homogenization section, feeding halogen flame retardant and flame retardant auxiliary agent at a second feeding port of the melting homogenization section, and extruding and granulating by a twin screw extrusion stage to obtain the dynamically vulcanized thermoplastic elastomer material.
Preferably, the preparation is carried out by using one of an intermeshing co-rotating twin-screw extruder or an intermeshing counter-rotating twin-screw extruder, the length-diameter ratio of the twin-screw extruder is 35-96, the melting and homogenizing section comprises 10-30 barrels, and the temperature of the twin-screw extruder is set as follows: the feeding section is 70-150 ℃, the melting homogenization section is 160-210 ℃, the head is 180-200 ℃, the screw rotating speed of the double-screw extruder is 250-800rpm, and 1 feeding port and 2 feeding ports for adding raw materials are respectively arranged on the feeding section and the melting homogenization section.
Preferably, the first feeding port of the melting and homogenizing section is positioned at 1/5 to 1/3 cylinder of the total cylinder of the melting and homogenizing section, and the second feeding port of the melting and homogenizing section is positioned at 1/2 to 4/5 cylinder of the total cylinder of the melting and homogenizing section.
The content of the rubber phase in the dynamically vulcanized thermoplastic elastomer system (usually more than 50 percent) is much higher than that of the thermoplastic resin, the selection amount and the preparation process of the cross-linking agent and the auxiliary cross-linking agent, and the cross-linking of the rubber phase and the subsequent more important phase inversion are directly influenced, namely the initial continuous rubber phase is dispersed in the system to form a sea-island structure. In the crosslinking process, the crosslinking agent is mainly used for forming active sites in a rubber phase chain segment, and the auxiliary crosslinking agent is a multifunctional compound to realize chemical bond combination between the active sites.
The invention further relates to the application of the high-flame-retardant low-gloss dynamically vulcanized thermoplastic elastomer material in preparing automobile interior parts.
The invention has the beneficial effects that:
(1) The invention unexpectedly discovers that the ethylene-butylene elastomer is selected to replace the traditional rubber, so that the preparation process of the dynamically vulcanized thermoplastic elastomer can be effectively simplified, the processing and production efficiency is greatly improved, more importantly, the glass transition temperature of the ethylene-butylene elastomer is lower than minus 50 ℃, the impact resistance of the material can be remarkably improved, and the impact resistance of the material can be improved under the condition of the existence of a flame retardant;
(2) The invention also unexpectedly discovers that when the ethylene content of the polypropylene material compounded by ethylene-propylene block copolymerization polypropylene and homopolymerized polypropylene is 10-40%, the material has good impact resistance and rigidity, and the mechanical property of the material can be ensured in the presence of a large amount of flame retardant;
(3) The invention also unexpectedly discovers that the preferable combination of the flame retardant with the specific structure and the anti-dripping agent can endow the dynamically vulcanized thermoplastic elastomer with excellent flame retardant performance, can still reach V0 grade under the condition of 0.8mm thickness, and the material still has good impact resistance so as to meet the material requirements of the automobile industry and the like;
(4) More remarkably, the invention adopts polyethylene wax to improve the reflectivity of the material and the dispersion of silicon dioxide, particularly the lipophilic silicon dioxide can enhance the light scattering effect, the compatibility of the special lipophilic modified silicon dioxide and the polyolefin material is greatly improved, and the special lipophilic modified silicon dioxide can be well migrated to the surface of the material to play a role in scattering light, and the polyethylene wax and the lipophilic silicon dioxide are compounded for use so as to obviously reduce the glossiness of the material;
(3) The preparation method provided by the invention removes the crushing and mixing processes in the traditional process, only adds two feeding ports to inject the cross-linking agent, the auxiliary cross-linking agent and the composite flame retardant in the melting and homogenizing section of the material extrusion process, simplifies the process, greatly reduces the preparation time, has low extrusion temperature in the whole process, consumes less energy, greatly reduces the production cost, and is very suitable for large-scale process production.
Drawings
FIG. 1 is a schematic view of a continuous process for producing a dynamically vulcanized thermoplastic elastomer according to the present invention.
Wherein 1 is double screw extruder driving motor, 2 is the feed inlet of feeding section, 3 is the first feed inlet of melting homogenization section, 4 is the second feed inlet of melting homogenization section, 5 is the feeding section, 6 is the melting homogenization section, and 7 is the aircraft nose.
FIG. 2 is a Scanning Electron Microscope (SEM) picture of a high flame retardant low gloss dynamically vulcanized thermoplastic elastomer material prepared in example 1.
FIG. 3 is a Scanning Electron Microscope (SEM) picture of a high flame retardant low gloss dynamically vulcanized thermoplastic elastomer material prepared in example 2.
FIG. 4 is a Scanning Electron Microscope (SEM) picture of a high flame retardant low gloss dynamically vulcanized thermoplastic elastomer material prepared in example 3.
FIG. 5 is a Scanning Electron Microscope (SEM) picture of a high flame retardant low gloss dynamically vulcanized thermoplastic elastomer material prepared in example 4.
Detailed Description
The preparation process provided by the present invention is further illustrated in detail by the following examples, but the present invention is not limited thereto.
The features, benefits and advantages of the present invention will become apparent to those skilled in the art from a reading of the present disclosure. All percentages, parts and ratios are based on the total weight of the composition of the present invention, unless otherwise specified. All weights as they pertain to listed ingredients are assigned to levels of active material and, therefore, do not include solvents or by-products that may be included in commercially available materials, unless otherwise specified. The term "weight content" herein may be represented by the symbol "%".
All formulations and tests herein occur at 25 ℃ environment, unless otherwise indicated.
The use of "including," "comprising," "containing," "having," or other variations thereof herein, is meant to encompass the non-exclusive inclusion, as such terms are not to be construed. The term "comprising" means that other steps and ingredients can be added that do not affect the end result. The term "comprising" also includes the terms "consisting of …" and "consisting essentially of …". The compositions and methods/processes of the present invention can comprise, consist of, and consist essentially of the essential elements and limitations described herein, as well as any of the additional or optional ingredients, components, steps, or limitations described herein.
Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The following examples are intended to further describe and demonstrate embodiments within the scope of the present invention. The examples are therefore to be understood as merely illustrative of the invention in more detail and not as limiting the content of the invention in any way. In the following examples, all amounts are by weight unless otherwise indicated, and the amounts of the listed ingredients are converted to active material amounts.
Melt flow index (MFR) test method: according to the test standard ASTM D1238, a double-display intelligent temperature control instrument is adopted, the temperature control precision is stable, and the melt index of the functional polyolefin material is tested under the test conditions of 230 ℃ and 2.16Kg. The higher the melt flow index, the lower the sample melt viscosity and the better the flowability.
The mechanical property testing method comprises the following steps: mechanical bars of the corresponding dimensions were injection-molded according to Table 1 and tested after conditioning for 48h in a standard environment (23 ℃,50% relative humidity). Wherein tensile, bending and izod notched impact spline dimensional requirements are shown in table 1.
TABLE 1 mechanical spline size requirements
| Spline name | Sample size (mm) |
| Tensile sample strip | 150 (Length). Times.10 (Width). Times.4 (thickness) |
| Curved spline | 80 (Length). Times.10 (width). Times.4 thickness) |
| Notched impact bar for cantilever beam | 80 (Length). Times.10 (Width). Times.4 (thickness) |
Tensile strength, tensile modulus and elongation at break tests were performed according to ISO527 standard; flexural strength and flexural modulus tests were performed according to ISO178 standard; notched izod impact strength was performed according to ISO180 standards.
The flame retardant property test method comprises the following steps: the injection-molded specimens having dimensions of 100X 10X 0.8mm were tested in accordance with UL-94 standard after conditioning for 48 hours in a standard environment (23 ℃ C., 50% relative humidity). The sample strips are vertically placed, the sample strips can be extinguished within 10s after ignition, the grade V0 is that the cotton wool can not be ignited by the droppings, the sample strips are vertically placed, the grade V1 is that the cotton wool can not be ignited by the droppings, and the grade V2 is that the cotton wool can be ignited by the droppings.
Gloss (Gloss) test method: the test was carried out on smooth plates using a gloss meter at 60 ℃ according to test standard ISO 2813.
Crosslinking agent
Dicumyl peroxide, analytically pure, purchased from the Chinese pharmaceutical group;
di-tert-butyl peroxide, analytically pure, purchased from alatin reagent;
2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, analytically pure, purchased from the Chinese pharmaceutical group;
azobisisobutyronitrile, analytically pure, was purchased from the avadin reagent.
Auxiliary crosslinking agent
Glycidyl methacrylate, analytically pure, purchased from the Chinese pharmaceutical group;
triallyl isocyanurate, analytically pure, purchased from avastin reagent;
trimethylolpropane triacrylate, analytically pure, purchased from alatin reagent;
stilbene, analytically pure, purchased from the group of Chinese medicines.
Polypropylene
Polypropylene, pellets, PP-MN15, homo-polypropylene, from the Luoyang petrochemical industry, having a melt flow index of 230 ℃, a test value of 15g/10min at 2.16KG, and an ethylene content of 0;
polypropylene, granular material, K7760, block copolymerized polypropylene, available from the medium petrochemical Yanshan petrochemical, having a melt flow index of 230 ℃, a test value of 60g/10min at 2.16KG, and an ethylene content of 5%;
polypropylene, pellets, BX3950, block copolypropylene, available from SK chemistry, having a melt flow index of 230 ℃, a test value of 150g/10min at 2.16KG, an ethylene content of 5%;
polypropylene, pellets, SP179, block copolypropylene, available from the petroleum company of Ziru, having a melt flow index of 230 ℃ and a test value of 8g/10min at 2.16KG, and an ethylene content of 15%.
Ethylene-butene elastomers
Ethylene-butene elastomer, pellets, engage7467, available from dow chemical, having a melt flow index of 190 ℃, a test value of 1.0g/10min at 2.16KG, a glass transition temperature of-58 ℃;
ethylene-butene elastomer, pellets, engage7447, from dow chemical, having a melt flow index of 190 ℃, a test value of 5.0g/10min at 2.16KG, a glass transition temperature of-53 ℃;
ethylene-butene elastomer, pellets, engage7280, available from dow chemical, having a melt flow index of 190 ℃, a test value of 0.5g/10min at 2.16KG, a glass transition temperature of-46 ℃;
ethylene-butene elastomer, pellets, engage7277, available from mitsui chemistry, having a melt flow index of 190 ℃, a test value of 0.8g/10min at 2.16KG, and a glass transition temperature of-44 ℃;
ethylene-butene elastomer, pellets, LC565, available from LG chemistry, having a melt flow index of 190 ℃, a test value at 2.16KG of 5.0g/10min, a glass transition temperature of-53 ℃;
ethylene-butene elastomer, pellets, A4050S, available from Mitsui Chemicals, had a melt flow index of 190 ℃, a test value of 5.0g/10min at 2.16KG, and a glass transition temperature of-53 ℃.
Flame retardant and anti-dripping agent
The flame retardant auxiliary agent is bismuth trioxide and arsenic trioxide, and the halogen-free flame retardant system is 1100DM (Qingyuan Pufu Fufu chemical Co., ltd.), which is a mixture of ammonium phosphate, pentaerythritol, melamine and derivatives thereof; the anti-dripping agent is zinc borate, silver borate, copper borate and nickel borate, and the anti-dripping agent is purchased from Abauba America.
Lubricant and antioxidant
The lubricant is polyethylene wax, ethylene bis fatty acid amide and pentaerythritol stearate, and is purchased from Liyang chemical industry; the antioxidant is hindered phenol type 1010 and phosphite type 168 available from BASF chemical.
Lipophilic silicon dioxide
Lipophilic silica 1: the median diameter D50 μm, the surface of which is grafted with siloxane groups, the specific molecular structure is shown as follows:
wherein R is 1 Is a hydrogen atom, R 2 The graft content of siloxane groups is 5% for methoxy groups.
Lipophilic silica 2: the median diameter D50 μm, the surface of which is grafted with siloxane groups, the specific molecular structure is shown as follows:
wherein R is 1 Is methyl, R 2 The graft content of siloxane groups is 20% for isobutoxy.
The preparation method of the high flame-retardant low-gloss dynamic vulcanization thermoplastic elastomer material comprises the following steps:
uniformly mixing ethylene-butylene elastomer, polypropylene, anti-dripping agent, lubricant and antioxidant, then feeding from a feeding port of a feeding section, uniformly mixing crosslinking agent and auxiliary crosslinking agent, then adding at a first feeding port of a melting homogenization section, adding a composite flame retardant comprising halogen flame retardant and flame retardant auxiliary agent from a second feeding port of the melting homogenization section, and carrying out extrusion granulation by a double screw extrusion stage to obtain the dynamically vulcanized thermoplastic elastomer material;
the double-screw extruder is a co-counter double-screw extruder, the length-diameter ratio of the double-screw extruder is 48, the melting homogenization section is provided with 20 sections of barrels, 1 and 2 feed inlets are respectively arranged in the feeding section and the melting homogenization section and used for adding raw materials, the first feed inlet of the melting homogenization section is positioned in the 5 th section of barrel, and the second feed inlet of the melting homogenization section is positioned in the 15 th section of barrel.
High flame retardant low gloss dynamically vulcanized thermoplastic elastomer materials examples 1-4 and comparative examples 1-2
The preparation of the materials of examples 1-4 and comparative examples 1-2 was completed according to the above-mentioned preparation method of high flame-retardant low-gloss dynamically vulcanized thermoplastic elastomer material, and the specific component ratios and material property results are shown in Table 2.
TABLE 2 component formulations and Properties of examples 1-4 and comparative examples 1-2
As shown in Table 2, examples 1-4 can successfully use the low glass transition temperature ethylene-butylene elastomer as the rubber phase for the preparation of dynamically vulcanized thermoplastic elastomer, and figures 2-5 are SEM pictures of the materials of examples 1-4, wherein the rubber phase is uniformly distributed in the matrix, the size of the rubber phase is 1-5 μm, and the normal temperature notched Izod impact property of the material is 35kJ/m 2 More importantly, after the halogen-containing flame retardant with the molecular structure is selected, the material can be extinguished within 10s after vertical ignition, droppings cannot ignite absorbent cotton below, and the flame retardance can reach the V0 level.
In the comparative examples 1-2, single block polypropylene copolymer or homo-polypropylene is used, the glass transition temperature of the ethylene-butylene elastomer is high, and the flame retardant adopts the traditional halogen-containing flame retardant and halogen-free flame retardant, so that the final material has generally low performance, the flexural modulus is below 700MPa, and the impact property is lower than 25kJ/m 2 The flame retardant grade is only V2, and the performance requirements of the flame retardant material for vehicles can not be met.
More surprisingly, the gloss of the materials can be reduced to within 1.5 after the polyethylene wax and the lipophilic silica are used in examples 1-4, and the gloss of the materials in comparative examples 1-2 is over 15 due to the absence of the lipophilic silica and the polyethylene wax, which shows that the materials of the present invention have a significant gloss reduction effect.
Comparative examples 3-4 of high flame retardance Low gloss dynamically vulcanized thermoplastic elastomer materials
According to the preparation method of the high-flame-retardant low-gloss dynamically vulcanized thermoplastic elastomer material, the preparation of the materials of comparative examples 3-4 is completed, and the difference between the comparative examples 3-4 and the example 1 is that the oleophylic modified silica 1 and the polyethylene wax are respectively and independently used, and the specific component ratio and the material performance results are shown in Table 3.
TABLE 3 comparative examples 3-4 component formulations and Properties
As shown in Table 3, compared with example 1, comparative examples 3 to 4 respectively use the oleophylic modified silica and the polyethylene wax separately, the difference between the mechanical property and the flame retardant property of the material is very small, mainly the gloss is greatly increased compared with the sample of example 1, which shows that the oleophylic modified silica and the polyethylene wax are required to be compounded for use for remarkable low-gloss effect, and the good low-gloss effect is difficult to obtain by single use.
High flame retardant Low gloss dynamically vulcanized thermoplastic elastomer materials examples 5-10
The preparation of the materials of examples 5-10 was completed according to the above-mentioned preparation method of the high flame retardant low gloss dynamically vulcanized thermoplastic elastomer material, and the specific component ratios and material property results are shown in Table 4.
Table 4 examples 5-10 component formulations and properties
As shown in examples 5-10, the related composition formula can be produced to obtain the dynamic vulcanization production with high flame retardant and low gloss, and has the advantages of excellent flame retardant property and impact resistance, low gloss, simple process and high production efficiency.
The invention unexpectedly discovers that the preparation process of the dynamic vulcanized thermoplastic elastomer can be effectively simplified by selecting the ethylene-butylene elastomer to replace the traditional rubber, the processing and production efficiency is greatly improved, and the mechanical property of the material can be improved by selecting the specific polypropylene material combination under the condition of the existence of the flame retardant. More importantly, the preferable combination of the composite flame retardant and the anti-dripping agent can endow the dynamic vulcanization thermoplastic elastomer with excellent flame retardant performance, the V0 grade can still be achieved under the condition of 0.8mm thickness, and the material still has good impact resistance and can meet the material requirements of the automobile industry and the like. Furthermore, considering the application of the material to automotive interiors, in order to avoid glare, the gloss can be significantly reduced by using special lipophilic silica and polyethylene wax to reduce the gloss of the material. In addition, the production process of the dynamic vulcanization thermoplastic elastomer has low energy consumption and greatly reduced production cost, and is very suitable for large-scale process production.
The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Unless otherwise stated, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40mm" is intended to mean "about 40mm".
Claims (13)
1. A high flame-retardant low-gloss dynamically vulcanized thermoplastic elastomer material is characterized in that: the melt flow index is 230 ℃, the test value is 2-40 g/10min under 2.16KG, the flame retardant grade is V0 under the condition that the thickness of a sample strip is 0.8mm, and the flame retardant grade comprises the following raw materials in parts by mass:
100 parts of ethylene-butylene elastomer;
30-75 parts of polypropylene;
0.5-8 parts of a crosslinking agent;
0.5-12 parts of lipophilic silicon dioxide;
0.5-8 parts of polyethylene wax;
0.05-4 parts of an auxiliary crosslinking agent;
10-55 parts of halogen flame retardant;
3-25 parts of a flame-retardant auxiliary agent;
0.5-12 parts of anti-dripping agent;
0.5-7 parts of a lubricant;
0.5 to 5 portions of antioxidant,
wherein the content of butylene in the ethylene-butylene elastomer is 20 to 50 percent, the melt flow index is 190 ℃, the test value under 2.16KG is 0.1 to 40g/10min, the glass transition temperature is lower than minus 50 ℃,
the halogen flame retardant has the following structural formula:
wherein R is 1 Is composed of
，/>
One of (1), R 2 Is one of oxygen atom, sulfur atom and selenium atom, R 3 Is one of fluorine atom, chlorine atom and bromine atom,
the flame-retardant auxiliary agent is one or two of bismuth trioxide and arsenic trioxide,
the polypropylene is a mixture of ethylene-propylene block copolymer polypropylene and homopolymerized polypropylene, and the anti-dripping agent is one of zinc borate, silver borate, copper borate and nickel borate.
2. The high flame retardant low gloss dynamically vulcanized thermoplastic elastomer material according to claim 1, wherein: the composite material comprises the following raw materials in parts by mass:
100 parts of ethylene-butylene elastomer;
35-70 parts of polypropylene;
1-5 parts of a cross-linking agent;
1-10 parts of lipophilic silicon dioxide;
1-5 parts of polyethylene wax;
0.1-2 parts of an auxiliary crosslinking agent;
15-50 parts of halogen flame retardant;
5-20 parts of a flame-retardant auxiliary agent;
1-10 parts of anti-dripping agent;
1-5 parts of a lubricant;
1-3 parts of an antioxidant.
3. The high-flame-retardant low-gloss dynamically vulcanized thermoplastic elastomer material as claimed in claim 1, wherein the ethylene-butylene elastomer has a crystallization temperature of 30 to 50 ℃ and a butylene content of 35 to 40%.
4. The highly flame-retardant low gloss dynamically vulcanized thermoplastic elastomer material according to claim 1 or 2, wherein the lipophilic silica has a median particle diameter D50 of 1-10 μm, and is surface-grafted with siloxane groups, and the specific molecular structure is as follows:
wherein R is 1 Is one of hydrogen atom and methyl, R 2 The siloxane group is one of methoxy, ethoxy, isopropoxy and isobutoxy, and the grafting content of the siloxane group is 1 to 20 percent; and/or
The polyethylene wax has a weight average molecular weight of 2000-10000 Dalton, a melt flow index of 230 ℃ and a test value of 300-1000g/10 min under 2.16KG.
5. The highly flame retardant, low gloss dynamically vulcanized thermoplastic elastomer material according to claim 4, wherein the graft content of siloxane groups is 1 to 5%.
6. The high-flame-retardant low-gloss dynamically vulcanized thermoplastic elastomer material as claimed in claim 1, wherein the polypropylene has a melt flow index of 230 ℃ and a test value of 20 to 150g/10min at 2.16KG, and the content of ethylene in the polypropylene is 10 to 40%.
7. The high flame retardant low gloss dynamically vulcanized thermoplastic elastomer material according to claim 1, wherein said crosslinking agent is one or a mixture of two or more of benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butylperoxycumene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, azobisisobutyronitrile, azobisisoheptonitrile,
the auxiliary crosslinking agent is one or a mixture of more than two of glycidyl methacrylate, N' -m-phenylene bismaleimide, triallyl isocyanurate, trimethylolpropane triacrylate, stannous chloride and diphenylethylene.
8. The high flame-retardant low-gloss dynamic vulcanization thermoplastic elastomer material according to claim 1, characterized in that a halogenated flame retardant system is formed by two parts, namely a halogenated flame retardant and a flame-retardant auxiliary agent, and the mass ratio of the halogenated flame retardant to the flame-retardant auxiliary agent is 5:1~2:1.
9. the high flame retardant low gloss dynamically vulcanized thermoplastic elastomer material according to claim 1, the method is characterized in that: the lubricant is one or a mixture of more than two of polyethylene wax, ethylene bis-fatty acid amide and pentaerythritol stearate, and the antioxidant is one or a mixture of two of hindered phenol antioxidant, thiodipropionic acid bis-ester antioxidant and phosphite antioxidant.
10. The continuous process for producing a highly flame-retardant, low-gloss dynamically vulcanized thermoplastic elastomer material according to any one of claims 1 to 9, which comprises mixing an ethylene-butene elastomer, a lipophilic silica, a polypropylene, a polyethylene wax, an anti-dripping agent, a lubricant and an antioxidant uniformly, feeding the mixture from a feed port of a feed section, mixing a crosslinking agent and a co-crosslinking agent uniformly, feeding the mixture from a first feed port of a melt-homogenizing section, feeding a halogenated flame retardant and a flame-retardant auxiliary agent from a second feed port of the melt-homogenizing section, and extruding the mixture through a twin-screw extruder to obtain a dynamically vulcanized thermoplastic elastomer material.
11. The continuous preparation method of claim 10, wherein the preparation is carried out by using one of a meshing co-rotating twin-screw extruder or a meshing counter-rotating twin-screw extruder, the length-diameter ratio of the twin-screw extruder is 35-96, the melting homogenization section comprises 10-30 sections of cylinders, and the temperature of the twin-screw extruder is set as follows: the feeding section is 70-150 ℃, the melting homogenization section is 160-210 ℃, the head is 180-200 ℃, the screw rotating speed of the double-screw extruder is 250-800rpm, and 1 feeding port and 2 feeding ports for adding raw materials are respectively arranged on the feeding section and the melting homogenization section.
12. The continuous preparation method of claim 11, wherein the first feeding port of the melting and homogenizing section is positioned at 1/5~1/3 cylinder of the total number of cylinders of the melting and homogenizing section, and the second feeding port of the melting and homogenizing section is positioned at 1/2~4/5 cylinder of the total number of cylinders of the melting and homogenizing section.
13. Use of a high flame retardant low gloss dynamically vulcanized thermoplastic elastomer material according to any one of claims 1 to 9 or obtained by the continuous production process according to any one of claims 10 to 12 for the production of automotive interior parts.
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