阅读说明：本技术 一种低voc、低烟密度的无卤阻燃耐磨型弹性卷材复合材料及其制备方法 (Low-VOC low-smoke-density halogen-free flame-retardant wear-resistant elastic coiled material composite material and preparation method thereof ) 是由 许锦树 刘敏 许雪平 于 2021-09-07 设计创作，主要内容包括：本发明公开了一种低VOC、低烟密度的无卤阻燃耐磨型弹性卷材复合材料及其制备方法,该复合材料包括以下重量份的组分：EVA共聚物5-20份、POE弹性体5-20份、TPU弹性体5-20份、增容剂1-10份、阻燃剂20-70份、抑烟剂5-15份、润滑剂0.5-2份、协效剂0.1-2份、偶联剂0.1-1份以及抗氧剂0.5-3份,兼具耐磨性和耐腐蚀性强、无卤阻燃效果好、烟密度低、有机挥发物被高效吸附脱除等优点,能满足高铁、动车等轨道交通对车厢内饰材料卷材地板的阻燃和环保要求；同时,该复合材料的制备工艺步骤简单、生产成本低、可操作性强,适合工业化生产,应用前景广阔。(The invention discloses a low-VOC, low-smoke density, halogen-free, flame-retardant and wear-resistant elastic coiled material composite material and a preparation method thereof, wherein the composite material comprises the following components in parts by weight: 5-20 parts of EVA copolymer, 5-20 parts of POE elastomer, 5-20 parts of TPU elastomer, 1-10 parts of compatibilizer, 20-70 parts of flame retardant, 5-15 parts of smoke suppressant, 0.5-2 parts of lubricant, 0.1-2 parts of synergist, 0.1-1 part of coupling agent and 0.5-3 parts of antioxidant, has the advantages of strong wear resistance and corrosion resistance, good halogen-free flame retardant effect, low smoke density, high-efficiency adsorption and removal of organic volatile matters and the like, and can meet the flame retardant and environmental protection requirements of rail traffic such as high-speed rail, motor train and the like on the coiled material floor of the interior trim material of the carriage; meanwhile, the preparation process of the composite material is simple in steps, low in production cost, strong in operability, suitable for industrial production and wide in application prospect.)

1. The halogen-free flame-retardant wear-resistant elastic coiled material composite material with low VOC and low smoke density is characterized by comprising the following components in parts by weight: 5-20 parts of EVA copolymer, 5-20 parts of POE elastomer, 5-20 parts of TPU elastomer, 1-10 parts of compatibilizer, 20-70 parts of flame retardant, 5-15 parts of smoke suppressant, 0.5-2 parts of lubricant, 0.1-2 parts of synergist, 0.1-1 part of coupling agent and 0.5-3 parts of antioxidant.

2. The low-VOC, low-smoke density, halogen-free, flame retardant, abrasion resistant elastic coil composite material according to claim 1, comprising the following components in parts by weight: 10-20 parts of EVA copolymer, 5-15 parts of POE elastomer, 5-15 parts of TPU elastomer, 1-8 parts of compatibilizer, 40-65 parts of flame retardant, 5-12 parts of smoke suppressant, 0.5-1.5 parts of lubricant, 0.1-1 part of synergist, 0.1-1 part of coupling agent and 0.5-2 parts of antioxidant.

3. The low-VOC, low-smoke density, halogen-free, flame retardant, abrasion resistant elastic coiled material composite material according to any of claims 1-2, wherein the EVA copolymer is ethylene-vinyl acetate; wherein the content of vinyl acetate is 20-50%, and the melt flow rate is 5-25 g/10 min.

4. The low-VOC, low-smoke density, halogen-free, flame retardant and wear resistant elastic coiled material composite material according to any one of claims 1-2, wherein the POE elastomer is a copolymer of ethylene and alpha-olefin; wherein the alpha-olefin is one or more of 1-butene, 1-hexene or 1-octene, the content is 20-30%, and the density is 0.862g/cm³～0.902g/cm³The melt flow rate is 0.5-5 g/10 min.

5. The low-VOC, low-smoke density, halogen-free, flame retardant and wear resistant elastic coiled material composite material as claimed in any one of claims 1-2, wherein the TPU elastomer is a polyester elastomer and/or a polyether elastomer, and the density is 1.10g/cm³～1.25g/cm³The Shore hardness is 60-80D.

6. The low-VOC, low-smoke-density, halogen-free, flame-retardant and wear-resistant elastic coiled material composite material as claimed in any one of claims 1-2, wherein the flame retardant is one or more of magnesium hydroxide, dolomite, phosphorus nitrogen flame retardant or piperazine pyrophosphate; the smoke suppressant is one or more of hydrotalcite, molybdenic acid or aluminum hydroxide.

7. The low-VOC, low-smoke-density, halogen-free, flame-retardant and wear-resistant elastic coiled material composite material as claimed in any one of claims 1-2, wherein the compatibilizer is one or more of SEBS, SEBS-g-MAH and PE-g-MAH.

8. The low-VOC, low-smoke density, halogen-free, flame retardant and wear resistant elastic coiled material composite material as claimed in any one of claims 1-2, wherein the lubricant is one or more of silicone master batch, G70S, stearic acid, EBS or polyethylene wax; the synergist is one or more of nano montmorillonite, nano attapulgite or synergist FR-18.

9. The low-VOC, low-smoke density, halogen-free, flame retardant and abrasion resistant elastic coiled material composite material according to any one of claims 1-2, wherein the coupling agent is one or more of KH-550, KH-560 or KH-570; the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant 168 or UV 328.

10. The preparation method of the low-VOC, low-smoke-density, halogen-free, flame-retardant and wear-resistant elastic coiled material composite material according to any one of claims 1 to 9, is characterized by comprising the following steps: (1) mixing a flame retardant, a smoke suppressant and a coupling agent in a high-speed mixer, wherein the mixing temperature is 85-100 ℃, and the mixing time is 8-15 minutes; (2) adding the main material, the compatibilizer and the mixture and uniformly mixing; (3) adding the material obtained in the step (2) into a main feed inlet of a Brinell mixer, and shearing, melting and mixing under the action of a screw; (4) uniformly mixing the lubricant, the synergist and the antioxidant, and adding the mixture into a second feed inlet of a Brinell mixer; (5) the vacuum degree of an exhaust port of the Brinell mixer is not lower than-0.08 MPa; (6) die bracing; (7) cutting into granules; (8) and (3) feeding the particles into a forced air drying bin, wherein the drying temperature is 120-140 ℃, and the drying time is 3-4 hours, so that the low-VOC, low-smoke-density, halogen-free, flame-retardant and wear-resistant elastic coiled material composite material is prepared.

Technical Field

The invention relates to the technical field of novel functional polymer materials, in particular to a low-VOC, low-smoke-density, halogen-free and flame-retardant wear-resistant elastic coiled material composite material and a preparation method thereof.

Background

With the rapid development of the construction of the high-speed railway in China, the rapid development of the manufacturing industry of rail transit equipment is driven, and a wide development prospect is brought to the high-speed railway interior material industry. The high-speed rail and the motor train are used as public transport means, have the characteristics of high speed, large and dense pedestrian volume, and the ground interior trim materials of the high-speed rail and the motor train must meet more strict flame-retardant and fireproof safety technical conditions so as to ensure the life safety of passengers.

The standard TB/T3237-2010 'technical conditions for flame retardance of interior materials for motor train units' stipulates that interior materials of railway rolling stock such as high-speed rails and the like meet the performance requirements of fire resistance, low smoke and low toxicity, and simultaneously, the influence of the air quality of a closed high-speed rail cabin on human health needs to be considered, the standard TB/T3139-.

The existing high-speed rail and motor car floor interior materials mainly use rubber or PVC floors, a large amount of plasticizer is required to be added in the processing process of the materials, the materials are influenced by the ambient temperature, the floor can be accelerated to release organic matters along with the rise of the temperature, and when VOC exceeds a certain concentration, headache, nausea, vomiting and limb weakness can be felt in a short time. If the patient is not away from the scene in time, the symptoms are aggravated, and in the severe cases, the patient can feel twitch and coma, so that the memory failure and other serious diseases are caused.

Secondly, various additives based on different metal compounds, which are generally contained in PVC flooring, generate metal-containing residues upon combustion, and for cost and performance reasons, PVC flooring further contains a large amount of inorganic fillers, such as calcium carbonate, clay, etc., which combine to release chlorine upon combustion of PVC flooring, forming a large amount of toxic and harmful substances such as black smoke and hydrogen chloride.

Patent CN107139558A discloses floor leather using melamine polyphosphate, melamine cyanurate, and alkyl aluminum hypophosphite as flame retardant, and this kind of phosphorus-nitrogen flame retardant system is easy to produce black smoke in the combustion process and difficult to meet the requirement of low smoke density.

Furthermore, the flooring material should be abrasion and scratch resistant, and its surface should have friction to facilitate walking. In summary, how to simultaneously realize low VOC, low smoke density, halogen-free flame retardant and wear resistance of the elastic coiled material floor is a difficult problem in the industry.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provide a low-VOC, low-smoke-density, halogen-free and flame-retardant wear-resistant elastic coiled material composite material and a preparation method thereof.

The technical scheme for solving the technical problems is as follows:

the invention provides a low-VOC, low-smoke-density, halogen-free, flame-retardant and wear-resistant elastic coiled material composite material which is characterized by comprising the following components in parts by weight: 5-20 parts of EVA copolymer, 5-20 parts of POE elastomer, 5-20 parts of TPU elastomer, 1-10 parts of compatibilizer, 20-70 parts of flame retardant, 5-15 parts of smoke suppressant, 0.5-2 parts of lubricant, 0.1-2 parts of synergist, 0.1-1 part of coupling agent and 0.5-3 parts of antioxidant;

preferably, 10-20 parts of EVA copolymer, 5-15 parts of POE elastomer, 5-15 parts of TPU elastomer, 1-8 parts of compatibilizer, 40-65 parts of flame retardant, 5-12 parts of smoke suppressant, 0.5-1.5 parts of lubricant, 0.1-1 part of synergist, 0.1-1 part of coupling agent and 0.5-2 parts of antioxidant;

further preferably, 15-20 parts of EVA copolymer, 6-12 parts of POE elastomer, 8-15 parts of TPU elastomer, 1-5 parts of compatibilizer, 50-65 parts of flame retardant, 5-10 parts of smoke suppressant, 0.8-1.2 parts of lubricant, 0.3-0.8 part of synergist, 0.3-0.8 part of coupling agent and 0.5-1 part of antioxidant;

further, the EVA copolymer is ethylene-vinyl acetate; wherein the content of vinyl acetate is 20-50%, and the melt flow rate (190 ℃, 2.16kg load) is 5-25 g/10 min;

further, the POE elastomer is a copolymer of ethylene and alpha-olefin; wherein the alpha-olefin is one or more of 1-butene, 1-hexene or 1-octene, the content is 20-30%, and the density is 0.862g/cm³～0.902g/cm³The melt flow rate is (190 ℃, 2.16kg of load) 0.5-5 g/10 min;

further, the TPU elastomer is a polyester elastomer and/or a polyether elastomer, and the density is 1.10g/cm³～1.25g/cm³The Shore hardness is 60-80D;

further, the flame retardant is one or more of magnesium hydroxide, dolomite, phosphorus nitrogen flame retardant or piperazine pyrophosphate, and the phosphorus nitrogen flame retardant is preferably CJ1003 or aluminum diethylphosphinate; the smoke suppressant is one or more of hydrotalcite, molybdenic acid and aluminum hydroxide;

further, the compatibilizer is one or more of SEBS, SEBS-g-MAH or PE-g-MAH;

further, the lubricant is one or more of silicone master batch, G70S, stearic acid, EBS or polyethylene wax;

further, the synergist is one or more of nano montmorillonite, nano attapulgite or synergist FR-18;

further, the coupling agent is one or more of KH-550, KH-560 or KH-570;

further, the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant 168 or UV 328;

the invention also provides a preparation method of the low-VOC low-smoke-density halogen-free flame-retardant wear-resistant elastic coiled material composite material, which is characterized by comprising the following steps of: (1) mixing a flame retardant, a smoke suppressant and a coupling agent in a high-speed mixer, wherein the mixing temperature is 85-100 ℃, and the mixing time is 8-15 minutes; (2) adding the main material, the compatibilizer and the mixture and uniformly mixing; (3) adding the material obtained in the step (2) into a main feed inlet of a Brinell mixer, and shearing, melting and mixing under the action of a screw; (4) uniformly mixing the lubricant, the synergist and the antioxidant, and adding the mixture into a second feed inlet of a Brinell mixer; (5) the vacuum degree of an exhaust port of the Brinell mixer is not lower than-0.08 MPa; (6) die bracing; (7) cutting into granules; (8) and (3) feeding the particles into a forced air drying bin, wherein the drying temperature is 120-140 ℃, and the drying time is 3-4 hours, so that the low-VOC, low-smoke-density, halogen-free, flame-retardant and wear-resistant elastic coiled material composite material is prepared.

The invention has the beneficial effects that: the composite material uses EVA copolymer, POE elastomer and TPU elastomer with different performances as main materials to ensure that the product has good wear resistance and corrosion resistance, and selects various auxiliary materials such as flame retardant, smoke suppressant, synergist and the like to match, so that the halogen-free flame retardant effect of the product is well coordinated and improved, and the smoke density of the product is greatly reduced; aiming at the problem that organic volatile matters are separated out in the using process of a product, the composite material physically adsorbs volatile small molecules in the material through an inorganic adsorbent hydrotalcite, and then volatilizes and removes the small molecular matters in the material through high temperature and negative pressure. Meanwhile, the preparation process of the composite material is simple in step, low in production cost, strong in operability and suitable for industrial production.

Drawings

FIG. 1: preparation process flow chart of low-VOC low-smoke-density halogen-free flame-retardant wear-resistant elastic coiled material composite material

Detailed Description

The invention is illustrated but not limited by the following examples. The technical solutions protected by the present invention are all the simple replacements or modifications made by the skilled person in the art.

Example 1:

metering flame retardants such as magnesium hydroxide, dolomite, phosphorus-nitrogen flame retardants and smoke suppressants according to the weight parts in the table 1, respectively adding the materials into a high-speed mixer for mixing, slowly dropwise adding a coupling agent when the temperature of the materials reaches 85-100 ℃, then mixing for 10 minutes, metering main materials and a compatibilizer according to the weight parts in the table 1, then adding the main materials and the compatibilizer into the high-speed mixer for mixing, adding the uniformly mixed materials into a main feed inlet of a Brinell mixer, then metering a lubricant, a synergist and an antioxidant according to the weight parts in the table 1, uniformly mixing, then adding the uniformly mixed materials into a second feed inlet of the Brinell mixer, shearing, melting and mixing under the action of a screw, wherein the processing temperature of the Brinell mixer is 130-180 ℃, the vacuum degree of an exhaust port of the Brinell mixer is not less than-0.08 MPa, feeding particles into a blast drying bin, the drying temperature is 120-140 ℃, and the drying time is 3-4 hours, thus obtaining the low VOC, The properties of the low-smoke-density halogen-free flame-retardant wear-resistant elastic coiled material composite material are shown in Table 2.

Table 1: raw material ratio (by weight) of halogen-free flame-retardant wear-resistant elastic coiled material with low VOC and low smoke density in each embodiment

Table 2: in each example, the performance parameters of the low VOC, low smoke density halogen-free flame retardant wear-resistant elastic coiled material composite material

Examples 2 to 5:

the preparation process of the halogen-free flame retardant wear-resistant elastic coiled material composite material with low VOC and low smoke density in the examples 2-5 is the same as that in the example 1, and only the raw material ratio is different, as shown in the table 1.

The performance parameters of the low VOC, low smoke density halogen free, flame retardant, abrasion resistant elastomeric web composites of examples 2-5 are shown in Table 2.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept of the present invention, and these changes and modifications are all within the scope of the present invention. The invention is illustrated but not limited by the following examples. The technical solutions protected by the present invention are all the simple replacements or modifications made by the skilled person in the art.