CN115558204B - Low-shrinkage high-gloss V0-grade halogen-free flame-retardant polypropylene composite material and preparation method thereof - Google Patents
Low-shrinkage high-gloss V0-grade halogen-free flame-retardant polypropylene composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of high polymer materials, in particular to a low-shrinkage high-gloss V0-level halogen-free flame-retardant polypropylene composite material and a preparation method thereof. Wherein, the raw materials of the low-shrinkage high-gloss V0-level halogen-free flame-retardant polypropylene composite material comprise 21.8 to 41.8 weight percent of homo-polypropylene, 15 weight percent of co-polypropylene, 3 weight percent of toughening agent, 2 weight percent of compatilizer, 26 weight percent of halogen-free flame retardant, 10 to 30 weight percent of modified whisker master batch, 0.4 weight percent of antioxidant, 0.6 weight percent of lubricant, 1 to 5 weight percent of hyperdispersant and 0.2 weight percent of flame-retardant synergist. The low-shrinkage high-gloss V0-level halogen-free flame-retardant polypropylene composite material prepared by the invention has the characteristics of small shrinkage, good apparent effect, excellent comprehensive mechanical property and accordance with the flame-retardant level of UL94 vertical burning 1.6mmV0, and can meet the use requirements of being used as an appearance part, requiring good dimensional stability and contacting with an electronic device.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a low-shrinkage high-gloss V0-level halogen-free flame-retardant polypropylene composite material and a preparation method thereof.
Background
The polypropylene resin raw material has the characteristics of good comprehensive mechanical property, high heat-resistant temperature, excellent electrical insulation property and chemical stability to acid and alkali, wide production and processing window, low price and the like, so that the polypropylene resin raw material is widely applied to the fields of household articles, electronic appliances and the like. However, because the polypropylene has low oxygen index, only about 18 percent, is easy to burn, and can easily cause fire when certain elements in electronic products are locally overheated due to poor contact, overload or short circuit and the like, the polypropylene needs to be subjected to flame retardant modification to have certain flame retardant property, and because the halogen-free flame retardant has small smoke during burning, the halogen-free flame retardant is generally required to be used for modifying the polypropylene to be used as a flame retardant material for vertical burning V0 level at present; meanwhile, as some products have larger size or thicker glue positions, materials are required to have smaller shrinkage rate so that the final product meets the size requirement and the appearance requirement; in addition, when the product is used as an appearance part, the material is required to have certain glossiness. Therefore, the development of V0 grade halogen-free flame retardant polypropylene composite materials with low shrinkage and good appearance luster becomes a real demand.
Chinese patent CN109721836A discloses a flame-retardant shading low-shrinkage polypropylene composite material and a preparation method thereof, and mineral fibers, glass fibers, titanium pigment and other additives are added to endow polypropylene with low shrinkage and shading performance, however, with the addition of the glass fibers, the appearance gloss of the material is poor, and the flame retardance can only achieve the V2 level of vertical combustion.
Chinese patent CN108485065A discloses a low-shrinkage polypropylene material and a preparation method thereof, and additives such as calcium carbonate, talcum powder and magnesium hydroxide are added to endow polypropylene with low shrinkage and flame retardant property, however, the surface effect of the material is not mentioned, and the flame retardant efficiency of magnesium hydroxide is low, so that the material can only realize horizontal combustion of less than 75mm/min in flame retardant aspect, and cannot realize vertical combustion V0-level flame retardant.
Chinese patent CN110964256a discloses a high-efficiency halogen-free intumescent flame retardant glass fiber reinforced polypropylene material and a preparation method thereof, which endows polypropylene with low shrinkage property through glass fiber modification, however, the surface gloss of the material can be greatly affected due to the addition of glass fiber.
Disclosure of Invention
In order to solve the defects of low flame retardant efficiency and poor glossiness of the existing polypropylene material, the invention provides a low-shrinkage high-gloss V0-level halogen-free flame retardant polypropylene composite material, which comprises the following raw materials in percentage by weight:
21.8 to 41.8 weight percent of homo-polypropylene, 15 weight percent of co-polypropylene, 3 weight percent of toughening agent, 2 weight percent of compatilizer, 26 weight percent of halogen-free flame retardant, 10 to 30 weight percent of modified whisker master batch, 0.4 weight percent of antioxidant, 0.6 weight percent of lubricant, 1 to 5 weight percent of hyperdispersant and 0.2 weight percent of flame retardant synergist.
In one embodiment, the homo-polypropylene is high isotacticity homo-polypropylene, the isotacticity is more than or equal to 96%, and the melt index is less than 5g/10min. Preferably, the homo-polypropylene is PP501SF from Fujian United petrochemical industry.
In one embodiment, the polypropylene copolymer is medium-melt high-resistance block copolymerized polypropylene, the melt flow rate (230 ℃ C., 2.16 kg) is 5-15 g/10min, and the notched impact of the simply supported beam is more than 20KJ/m 2 . Preferably, the polypropylene copolymer is PP SP179, petrochemical in lanzhou.
In one embodiment, the toughener melt flow rate (190 ℃,2.16 kg) is greater than 20g/10min. Preferably, the toughening agent is us Tao Shigao fluidity POE8402.
In one embodiment, the compatibilizing agent is an optical polypropylene grafted maleic anhydride GPM-200A.
In one embodiment, the modified whisker master batch is a self-made modified whisker master batch NP-S04-L-M61776, and the preparation process comprises the following steps: pouring deionized water at 60 ℃ into a beaker filled with (7-octen-1-yl) trimethoxysilane according to the mass ratio of (7-octen-1-yl) trimethoxysilane to deionized water of 1:3, and standing for 1h until the deionized water is hydrolyzed for later use; adding polypropylene resin powder into a high-speed mixer heated to 80 ℃, then adding hydrolyzed (7-octen-1-yl) trimethoxysilane, stirring at a high speed of 300r/min for 3 minutes, and soaking and uniformly distributing the hydrolyzed (7-octen-1-yl) trimethoxysilane on the surface of the polypropylene resin; then adding calcium sulfate whisker powder, and stirring at a low speed of 100r/min for 5 minutes. And then adding the mixed material into a single screw extruder, and carrying out melting, extrusion bracing and granulating to obtain the modified whisker master batch NP-S04-L-M61776.
In one embodiment, the weight ratio of the polypropylene resin powder, the hydrolyzed (7-octene-1-radical) trimethoxysilane and the calcium sulfate whisker powder is (1-5): (0.01-0.1): (1-5).
In one embodiment, the calcium sulfate whisker powder has a particle length of 10-100 μm (90%), a diameter of 1-10 μm (90%), and an aspect ratio of 5-40 (90%); the purity of the (7-octen-1-yl) trimethoxysilane is more than 90 percent. Preferably, the calcium sulfate whisker powder is of the Shanghai Pelargonium NP-S04-L model, and the (7-octen-1-yl) trimethoxysilane is of the Shanghai Michael chemical technology Co., ltd M61776.
In one embodiment, the antioxidant is one or more of a hindered phenolic antioxidant, a thioester antioxidant, and a phosphite antioxidant.
In one embodiment, the lubricant is one or more of polyethylene wax, polypropylene wax, calcium stearate, ethylene bis fatty acid amide, zinc stearate, and magnesium stearate.
In one embodiment, the hyper-dispersant is Shanghai hucho taimen DP-1000.
In one embodiment, the flame retardant synergist is high molecular polytetrafluoroethylene coated with acrylic acid, and the molecular weight is more than or equal to 300 ten thousand. Preferably, the flame retardant synergist is Guangzhou entropy energy SN3306.
The invention also provides a preparation method of the low-shrinkage high-gloss V0-level halogen-free flame-retardant polypropylene composite material, which comprises the following steps:
(1) Weighing homo-polypropylene, co-polypropylene, a toughening agent, a compatilizer, a halogen-free flame retardant, an antioxidant, a lubricant, a hyperdispersant and a flame retardant synergist according to weight percentage;
(2) Adding all materials in the step (1) into a high-speed stirrer, and stirring and mixing at a high speed uniformly to obtain a premix;
(3) Adding the premix obtained in the step (2) into a parallel double-screw extruder from a main feeding hopper, and simultaneously adding the modified whisker master batch into the parallel double-screw extruder from a side feeding port, so that all component materials are subjected to shearing, melting, blending and extrusion in the parallel double-screw extruder, wherein the processing temperature of the double-screw extruder is 170-190 ℃;
(4) And cooling, drying and granulating the material strips discharged from the die of the parallel double-screw extruder to obtain the low-shrinkage high-gloss V0-level halogen-free flame-retardant polypropylene composite material.
Based on the above, compared with the prior art, the invention has the following beneficial effects:
1. the invention improves the dispersibility of the whisker in the polypropylene resin and enhances the binding force of the whisker and the polypropylene resin by a method of specially modifying the whisker master batch, and improves the overall performance of the composite material. After the (7-octene-1-yl) trimethoxysilane is hydrolyzed, three methoxy groups in the molecule are respectively substituted by hydroxyl groups to have polarity, and the surface of the inorganic filler whisker placed in the naked air is also provided with a certain polarity due to the adsorption of a thin water layer. At this time, the hydroxyl groups on the hydrolyzed (7-octen-1-yl) trimethoxysilane molecules and the moisture on the whisker surface are bridged by intermolecular hydrogen bonds, and the other end of the (7-octen-1-yl) trimethoxysilane molecules is bonded with the polypropylene molecular chain by physical bonding and winding of the 7-octen-1-yl methylene long chain molecules, so that the (7-octen-1-yl) trimethoxysilane bonds the polypropylene resin with the whisker.
2. The modified whisker master batch adopted by the invention prevents the aggregation of whisker powder, avoids the damage to the structure with high length-diameter ratio caused by strong shearing stress due to aggregation in the subsequent double-screw blending extrusion granulation process, and maintains the enhancement effect of the whisker with high length-diameter ratio on polypropylene resin to the greatest extent; the (7-octene-1-yl) trimethoxysilane is used as a lubricating layer for coating the whisker, so that the shearing force of the twin screw on the whisker can be effectively weakened, the breakage probability of the whisker is reduced, the high length-diameter ratio is maintained, and the good enhancement effect of the whisker on the polypropylene resin is maintained; the compatibility of the whisker and polypropylene can be increased by coating the whisker with (7-octene-1-yl) trimethoxysilane, the binding force of the whisker and the polypropylene interface can be improved, and the overall mechanical property of the final composite material can be improved.
3. The super-dispersing agent adopted by the invention is a super-dispersing flow improving auxiliary agent based on nano-base, the dispersing effect of inorganic filler in polypropylene resin is improved through the super-dispersibility of the nano-base, the melt fluidity is improved, the plastic is evenly plasticized at a relatively low temperature, the appearance defects such as flow marks, pinholes, surface roughness and the like are avoided, and the surface gloss of the plastic product is improved.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure and/or components pointed out in the written description and claims.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the following description will be made in conjunction with the technical solutions in the embodiments of the present invention, and it is apparent that the described embodiments are some, but not all, embodiments of the present invention; the technical features designed in the different embodiments of the invention described below can be combined with each other as long as they do not conflict with each other; all other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present invention, it should be noted that all terms used in the present invention (including technical terms and scientific terms) have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs and are not to be construed as limiting the present invention; it will be further understood that terms used herein should be interpreted as having a meaning that is consistent with their meaning in the context of this specification and the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Example 1
The preparation method of the modified whisker master batch NP-S04-L-M61776 comprises the following steps: (1) Pouring deionized water at 60 ℃ into a beaker filled with (7-octene-1-yl) trimethoxysilane according to the mass ratio of (7-octene-1-yl) trimethoxysilane to deionized water of 1:3, and standing for 1h until the deionized water is hydrolyzed for later use; (2) Adding 2 parts of polypropylene resin powder into a high-speed mixer which is heated to 80 ℃ in parts by weight, then adding 0.02 part of hydrolyzed (7-octen-1-yl) trimethoxysilane, and stirring at a speed of 300r/min for 3 minutes at a high speed to infiltrate and uniformly distribute the hydrolyzed (7-octen-1-yl) trimethoxysilane on the surface of the polypropylene resin; then, 1 part of calcium sulfate whisker powder was added thereto, and the mixture was stirred at a low speed of 100r/min for 5 minutes. And then adding the mixed material into a single screw extruder, and carrying out melting, extrusion bracing and granulating to obtain the modified whisker master batch NP-S04-L-M61776 for later use.
Then, weighing corresponding raw materials according to the parts by weight in the table 1;
uniformly mixing the weighed homo-polypropylene, co-polypropylene, toughening agent, compatilizer, halogen-free flame retardant, antioxidant, lubricant, hyperdispersant and flame retardant synergist, adding the mixture into a parallel double-screw extruder from a main feeding port, and simultaneously adding modified whisker master batch into the parallel double-screw extruder from a side feeding port, so that all component materials are subjected to shearing, melting, blending and extrusion in the parallel double-screw extruder, wherein the processing temperature of the double-screw extruder is one area 170 ℃, two areas 180 ℃, three areas 190 ℃, four areas 190 ℃, five areas 190 ℃, six areas 180 ℃, seven areas 180 ℃, eight areas 180 ℃, nine areas 180 ℃, ten areas 180 ℃ and a machine head 190 ℃; and finally, cooling, drying and granulating the material strips discharged from the die of the parallel double-screw extruder to obtain the low-shrinkage high-gloss V0-level halogen-free flame-retardant polypropylene composite material.
Table 1 dosage forms for each example and comparative example
Example 2
The corresponding raw materials were weighed according to the parts by weight described in table 1 and the preparation method was the same as in example 1.
Example 3
The corresponding raw materials were weighed according to the parts by weight described in table 1 and the preparation method was the same as in example 1.
Example 4
The corresponding raw materials were weighed according to the parts by weight described in table 1 and the preparation method was the same as in example 1.
Comparative example 1
The corresponding raw materials were weighed according to the parts by weight described in table 1 and the preparation method was the same as in example 1.
Comparative example 2
The corresponding raw materials were weighed according to the parts by weight described in table 1, the preparation method was the same as in example 1, and the experimental results are shown in table 2.
Comparative example 3
The corresponding raw materials were weighed according to the parts by weight described in table 1 and the preparation method was the same as in example 1.
Comparative example 3 differs from example 4 in that the modified whisker master batch used in comparative example 3 was homemade NP-S04-L-CG-8830, and the modified whisker master batch NP-S04-L-CG-8830 differed from the modified whisker master batch NP-S04-L-M61776 in example 4 only in that the treating agent of NP-S04-L-M61776 was (7-octen-1-yl) trimethoxysilane M61776, and the treating agent of NP-S04-L-CG-8830 was octyl trimethoxysilane CG-8830. The proportion of the whole components of the modified whisker master batch is unchanged.
The following tests were carried out on the results of the above examples and comparative examples: tensile strength, notched impact strength of a simply supported beam, vertical burn performance, shrinkage, and color appearance. The specific experimental results are shown in Table 2.
Specific detection methods of tensile strength, notched impact strength of a simply supported beam, vertical combustion performance and shrinkage rate refer to standard detection, and are not repeated here; the color plate appearance detection method comprises the following steps: and (3) injecting the highlight color plate by using a highlight color plate mold, observing the surface condition of the color plate, and scoring according to the following standard, wherein the higher the score is, the better the appearance condition is.
5, the method comprises the following steps: the whole surface of the color plate is uniform and smooth, and has good luster;
4, the following steps: the whole surface of the color plate is uniform and smooth, and the luster is general;
3, the method comprises the following steps: the whole surface of the color plate is uniform and smooth and has slight luster;
2, the method comprises the following steps: the whole surface of the color plate is uniform and smooth, but is rough;
1, the method comprises the following steps: the whole surface of the color plate is uneven and has obvious wavy lines;
table 2 table of experimental results for each example and comparative example
It should be noted that the specific parameters or some common reagents in the above embodiments are specific embodiments or preferred embodiments under the concept of the present invention, and are not limited thereto; and can be adaptively adjusted by those skilled in the art within the concept and the protection scope of the invention.
In addition, unless otherwise specified, the starting materials employed may also be commercially available products conventionally used in the art or may be prepared by methods conventionally used in the art.
By combining the tables 1 and 2, as can be seen from the comparison of the examples 1 and 2, as the proportion of the components NP-S04-L-M61776 of the modified whisker master batch increases, the shrinkage of the polypropylene molecular chain can be well inhibited due to the fact that the whisker has a larger length-diameter ratio, and the shrinkage rate of the composite material is obviously reduced; as can be seen from a comparison of example 1 and example 3, as the proportion of the hyperdispersant component increases, the dispersibility of the modified whisker master batch further improves, and the gloss of the composite material becomes better; as can be seen from the comparison between the comparative example 1 and the example 4, the polypropylene molecular chain is not inhibited without the modified whisker master batch NP-S04-L-M61776, so that the composite material has great shrinkage rate due to crystallization, and the dimensional stability of the material in the practical use process is poor; as can be seen from the comparison between the comparative example 2 and the example 4, the dispersion uniformity of the modified whisker master batch NP-S04-L-M61776 and the flame retardant can be affected to a certain extent without adding the hyper-dispersant, thereby affecting the appearance effect of the composite material; as can be seen from the comparison of comparative example 3 and example 4, octyl trimethoxy silane CG-8830 is used for replacing (7-octene-1-yl) trimethoxy silane M61776 as a treating agent for the modified whisker master batch, and because one end of the octyl trimethoxy silane linked with polypropylene consists of a methylene-methyl structure, the methylene-methyl structure molecular chain has good flexibility and is easy to slip when being stretched and stressed; the end of the (7-octene-1-yl) trimethoxysilane linked with the polypropylene is composed of a methylene-olefinic bond (double bond) structure, the double bond structure at the tail end is relatively high in rigidity, the conformation is not easy to change when the stress is applied, so that the bond between the whisker and the polypropylene is high, and the overall mechanical property of the final composite material is high.
In conclusion, by adopting the technical scheme of the invention, the prepared low-shrinkage high-gloss V0-level halogen-free flame-retardant polypropylene composite material has the characteristics of small shrinkage, good apparent effect, excellent comprehensive mechanical property and compliance with the UL94 vertical burning 1.6mmV0 flame-retardant level, can be used as an appearance part, has good dimensional stability, can meet the use requirement of a product part related to the contact with an electronic device, and has good industrial application value.
In addition, it should be understood by those skilled in the art that although many problems exist in the prior art, each embodiment or technical solution of the present invention may be modified in only one or several respects, without having to solve all technical problems listed in the prior art or the background art at the same time. Those skilled in the art will understand that nothing in one claim should be taken as a limitation on that claim.
Although terms such as homo-polypropylene, co-polypropylene, toughening agents, compatibilizers, halogen-free flame retardants, modified whisker concentrates, antioxidants, lubricants, hyperdispersants, flame retardant synergists, etc. are more used herein, the possibility of using other terms is not precluded. These terms are used merely for convenience in describing and explaining the nature of the invention; they are to be interpreted as any additional limitation that is not inconsistent with the spirit of the present invention; the terms first, second, and the like in the description and in the claims, if any, are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (7)
1. The low-shrinkage high-gloss V0-grade halogen-free flame-retardant polypropylene composite material is characterized by comprising the following raw materials in percentage by weight:
21.8 to 41.8 weight percent of homo-polypropylene, 15 weight percent of co-polypropylene, 3 weight percent of toughening agent, 2 weight percent of compatilizer, 26 weight percent of halogen-free flame retardant, 10 to 30 weight percent of modified whisker master batch, 0.4 weight percent of antioxidant, 0.6 weight percent of lubricant, 1 to 5 weight percent of hyperdispersant and 0.2 weight percent of flame retardant synergist;
the modified whisker master batch is a self-made modified whisker master batch NP-S04-L-M61776, and the preparation process comprises the following steps:
pouring deionized water at 60 ℃ into a beaker filled with (7-octen-1-yl) trimethoxysilane according to the mass ratio of (7-octen-1-yl) trimethoxysilane to deionized water of 1:3, and standing for 1h until the deionized water is hydrolyzed for later use; adding polypropylene resin powder into a high-speed mixer heated to 80 ℃, then adding hydrolyzed (7-octen-1-yl) trimethoxysilane, stirring at a high speed of 300r/min for 3 minutes, and soaking and uniformly distributing the hydrolyzed (7-octen-1-yl) trimethoxysilane on the surface of the polypropylene resin; then adding calcium sulfate whisker powder, and stirring at a low speed of 100r/min for 5 minutes; then adding the mixed material into a single screw extruder, and obtaining modified whisker master batch NP-S04-L-M61776 after melting, extruding and bracing and granulating;
the hyper-dispersant is Shanghai hucho taimen DP-1000; the compatilizer is photopolypropylene grafted maleic anhydride GPM-200A.
2. The low shrinkage high gloss V0 grade halogen free flame retardant polypropylene composite of claim 1, wherein: the homo-polypropylene is high isotacticity homo-polypropylene, the isotacticity is more than or equal to 96%, and the melt index is less than 5g/10min.
3. The low shrinkage high gloss V0 grade halogen free flame retardant polypropylene composite of claim 1, wherein: the polypropylene copolymer is medium-melt high-resistance block copolymerization polypropylene, and the melt flow rate is 5-15 g/10min, and is 2.16kg at 230 ℃; the notch impact of the simple beam is more than 20KJ/M 2 。
4. The low shrinkage high gloss V0 grade halogen free flame retardant polypropylene composite of claim 1, wherein: the weight ratio of the polypropylene resin powder to the hydrolyzed (7-octenyl-1-yl) trimethoxysilane to the calcium sulfate whisker powder is (1-5): (0.01-0.1): (1-5).
5. The low shrinkage high gloss V0 grade halogen free flame retardant polypropylene composite of claim 1, wherein: in the calcium sulfate whisker powder, 90% of the length is 10-100 mu m,90% of the diameter is 1-10 mu m, and 90% of the length-diameter ratio is 5-40; the purity of the (7-octen-1-yl) trimethoxysilane is more than 90 percent.
6. The low shrinkage high gloss V0 grade halogen free flame retardant polypropylene composite of claim 1, wherein: the antioxidant is one or a combination of more of hindered phenol antioxidants, thioester antioxidants and phosphite antioxidants; the lubricant is one or more of polyethylene wax, polypropylene wax, calcium stearate, ethylene bis fatty acid amide, zinc stearate and magnesium stearate.
7. A method for preparing the low-shrinkage high-gloss V0-grade halogen-free flame retardant polypropylene composite material according to any one of claims 1 to 6, which is characterized by comprising the following steps:
s100, weighing homo-polypropylene, co-polypropylene, a toughening agent, a compatilizer, a halogen-free flame retardant, an antioxidant, a lubricant, a hyperdispersant and a flame retardant synergist according to weight percentage;
s200, adding all materials in the step S100 into a high-speed stirrer, and stirring and mixing at a high speed uniformly to obtain a premix;
s300, adding the premix obtained in the step S200 into a parallel double-screw extruder from a main feeding hopper, and simultaneously adding the modified whisker master batch into the parallel double-screw extruder from a side feeding port, so that all component materials are subjected to shearing, melting, blending and extrusion in the parallel double-screw extruder, wherein the processing temperature of the double-screw extruder is 170-190 ℃;
s400, cooling, drying and granulating the material strips discharged from the die of the parallel double-screw extruder to obtain the low-shrinkage high-gloss V0-level halogen-free flame-retardant polypropylene composite material.
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