CN109337240B - Environment-friendly flame-retardant PVC/NBR (polyvinyl chloride/nitrile-butadiene rubber) foam material and preparation method thereof - Google Patents
Environment-friendly flame-retardant PVC/NBR (polyvinyl chloride/nitrile-butadiene rubber) foam material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an environment-friendly flame-retardant PVC/NBR (polyvinyl chloride/nitrile-butadiene rubber) foaming material and a preparation method thereof, wherein the material comprises 100 parts of PVC resin (emulsion polymerization)/NBR compound, 4-12 parts of composite foaming agent, 0.3-0.8 part of cross-linking agent, 1.8-2.5 parts of composite accelerator, 70-120 parts of composite halogen-free flame retardant, 25-40 parts of plasticizer, 2.0-4.0 parts of composite lubricant, 6-12 parts of reinforcing agent and 0.3-0.6 part of anti-aging agent. The environment-friendly flame-retardant PVC/NBR foam material has low smoke density, no toxicity and light specific gravity.
Description
Technical Field
The invention relates to a high polymer material and a preparation method thereof, in particular to an environment-friendly flame-retardant PVC/NBR foam material.
Background
The solubility parameters and polarities of the polyvinyl chloride (PVC) and the nitrile rubber (NBR) are similar, the compatibility of the polyvinyl chloride (PVC) and the nitrile rubber (NBR) is good, the blend of the polyvinyl chloride (PVC) and the nitrile rubber (NBR) is used as a matrix of the foaming material, so that the foaming product has the elasticity of the rubber foaming product and the good stiffness and the small shrinkage rate of the plastic foaming product, and the PVC has good flame retardance and weather resistance and can improve the defects of flammability and poor weather resistance of the NBR. The PVC/NBR blended material has excellent comprehensive performance. PVC/NBR foam materials have been widely used in air conditioning heat insulation pipes, sporting goods, life saving goods, vibration damping, heat insulation, sound insulation, and other applications.
At present, the PVC/NBR foaming material is mainly produced by adopting DOP or chlorinated paraffin as a plasticizer and calcium carbonate as filling. Because the flame retardant property of the PVC/NBR foam material is greatly reduced after a large amount of plasticizer is added, a large amount of smoke and toxic and harmful gas can be generated in the combustion process, and the calcium carbonate filler does not have the flame retardant function. Therefore, the PVC/NBR foam material can not meet the requirements of engineering fire-proof application in specific occasions.
Disclosure of Invention
The invention adopts the compound of active magnesium hydroxide and zinc borate as a flame retardant, adopts triphenyl phosphate or diphenyl isooctyl phosphate plasticizer with environment-friendly flame retardant effect to form a flame retardant system of the PVC/NBR foam material, so that the PVC/NBR foam material has excellent low-smoke and non-toxic environment-friendly performance, meets the RoHS instruction requirement issued by the European Union, has good mechanical property and flame retardant property, and can meet the requirements of the manufacturing application fields of indoor fireproof decoration, sound and heat insulation, air-conditioning copper pipe heat insulation materials and the like. One of the purposes of the invention is to solve the problems and provide an environment-friendly flame-retardant PVC/NBR foam material which has the advantages of simple and flexible use method, capability of meeting the production requirements of specific applications, better mechanical property, flame retardant property, sound and heat insulation and shock resistance, lower production cost and simple production process. The invention also aims to provide a preparation method of the environment-friendly flame-retardant PVC/NBR foam material.
The invention provides an environment-friendly flame-retardant foaming material which comprises the following components in parts by weight: 100 parts of PVC/NBR compound, 4-12 parts of composite foaming agent, 0.3-0.8 part of cross-linking agent, 1.8-2.5 parts of composite accelerator, 70-120 parts of composite halogen-free flame retardant, 25-40 parts of plasticizer, 2.0-4.0 parts of composite lubricant, 6-12 parts of reinforcing agent and 0.3-0.6 part of anti-aging agent.
The material of the invention preferably comprises the following components in parts by weight: 100 parts of PVC/NBR compound, 10 parts of composite foaming agent, 0.5 part of cross-linking agent, 2.1 parts of composite accelerator, 100 parts of composite halogen-free flame retardant, 30 parts of plasticizer, 2.5 parts of composite lubricant, 8 parts of reinforcing agent and 0.4 part of anti-aging agent.
Preferably, the PVC is emulsion polymerized PVC resin, and the PVC/NBR compound is composed according to the mass ratio of 1: 0.2-0.2: 1; the composite foaming agent is prepared from an AC foaming agent: ACP-W foaming agent: the zinc oxide is prepared according to the mass ratio of 12:1: 0.3-7: 1: 0.3; the cross-linking agent is sulfur; the composite lubricant is stearic acid: solid paraffin: the polyethylene glycol is prepared according to the mass ratio of 1:4: 2-1: 8: 4; the composite accelerator is DPTT: ZDBC: ZDEC: MBT is formed according to the mass ratio of 2:2:2: 1; the composite halogen-free flame retardant is active magnesium hydroxide: the zinc borate is prepared according to the mass ratio of 10: 1-20: 1; the plasticizer is triphenyl phosphate or diphenyl isooctyl phosphate, the reinforcing agent is carbon black, and the anti-aging agent is anti-aging agent RD or anti-aging agent DNP.
Preferably, the PVC/NBR compound of the invention is prepared according to the mass ratio of 1: 1.
The composite foaming agent of the invention is preferably prepared from an AC foaming agent: ACP-W foaming agent: the zinc oxide is composed according to the mass ratio of 8.7:1: 0.3.
The preferred composite lubricant of the present invention is stearic acid: solid paraffin: the polyethylene glycol is prepared according to the mass ratio of 1:4: 2.
The preferable composite halogen-free flame retardant of the invention is active magnesium hydroxide: the zinc borate is prepared according to the mass ratio of 15: 1;
the invention also provides a preparation method of the foaming material, which comprises the following steps:
(1) preparing PVC/NBR foam material high-temperature glue: weighing a composite foaming agent, a composite halogen-free flame retardant, a reinforcing agent, a composite lubricant, an anti-aging agent, a plasticizer and PVC resin according to a formula, sequentially feeding the materials into an internal mixer, wherein the rotating speed of a rotor of the internal mixer is 50n/min, the materials are internally mixed in the internal mixer, the materials are heated to 120 ℃ by self friction and discharged, the materials are mixed for 3-5 min by a double-roll open mill with the roll moment of 3-4 mm, thin-passing for 3 times for blanking, cooling into a sheet, cooling with cooling water by the double-roll open mill, and storing for 24-48 hours for later use to obtain the PVC/NBR foaming high-temperature adhesive;
(2) preparing the PVC/NBR foam material low-temperature adhesive:
weighing the environment-friendly flame-retardant PVC/NBR foaming material high-temperature adhesive obtained in the step (1), a crosslinking agent, a composite accelerator, a composite foaming agent and a plasticizer, pouring the materials into an internal mixer internal mixing chamber, carrying out internal mixing to 90-95 ℃ for about 5-6min, discharging for later use, carrying out open mixing by using an open mill for 2-3 min, wherein the roller spacing is 7-9 mm, carrying out thin passing for 3 times for discharging, and introducing cooling water into the open mill to obtain a PVC/NBR foaming low-temperature adhesive sheet;
(3) foaming and forming: and (3) performing foaming molding by using an oven, preheating the oven to 160-180 ℃, and then putting the PVC/NBR foamed low-temperature rubber sheet obtained in the step (2) into the oven to heat for 13-18 min to obtain the PVC/NBR foamed material.
The foaming material is applied to the fields of indoor fireproof decoration materials, sound and heat insulation materials and air-conditioning copper pipe heat insulation materials.
The invention has the following positive effects:
1. the compound of active magnesium hydroxide and zinc borate is used as a flame retardant and triphenyl phosphate or diphenyl isooctyl phosphate plasticizer with environment-friendly flame retardant effect to form a flame retardant system of the PVC/NBR foam material, so that the PVC/NBR foam material has excellent low-smoke and non-toxic environment-friendly performance, meets the RoHS instruction requirement issued by the European Union, has good mechanical property and flame retardant property, and has the characteristic of lower production cost.
2. A composite foaming system consisting of the AC foaming agent, the ACP-W foaming agent and the zinc oxide is beneficial to obtaining the PVC/NBR foaming material with uniform and stable cell size under the condition of a forming process.
3. Because the magnesium hydroxide is low in price, the production cost of the environment-friendly flame-retardant PVC/NBR foam material is reduced, and the market competitiveness of the product is improved.
4. Compared with the PVC/NBR foam material in the current market, the environment-friendly flame-retardant PVC/NBR foam material has good environment-friendly flame-retardant performance and meets the requirement of engineering fireproof application.
Detailed Description
The environment-friendly flame-retardant PVC/NBR foam material is prepared from the following components in parts by weight:
PVC resin: 5kg, NBR rubber: 5kg, 1kg of composite foaming agent (wherein, 0.87kg of AC foaming agent, 0.1kg of ACP-W foaming agent and 0.03kg of zinc oxide), crosslinking agent sulfur: 0.005kg, 0.02kg of composite lubricant (0.003 kg of stearic acid, 0.011kg of paraffin wax and 0.006kg of polyethylene glycol), 0.021kg of composite accelerator (0.021 kg of DPTT0.06kg, ZDBC 0.06kg, ZDEC 0.06kg and MBT0.03kg), composite halogen-free flame retardant: 10kg (wherein active magnesium hydroxide 9.3758kg, zinc borate 0.625kg), triphenyl phosphate plasticizer: 3kg, carbon black reinforcing agent: 0.08kg, antioxidant RD: 0.004 kg.
The preparation method of the environment-friendly flame-retardant PVC/NBR foam material comprises the following steps:
(1) preparing environment-friendly flame-retardant PVC/NBR foam material high-temperature adhesive:
weighing butadiene-acrylonitrile rubber, a composite halogen-free flame retardant, a reinforcing agent, a composite lubricant, an anti-aging agent, a plasticizer (accounting for 71 percent of the total amount of the plasticizer), and PVC resin according to a formula, and sequentially adding the materials into an internal mixer. The rotor speed of the internal mixer is 50 n/min. The materials are mixed in an internal mixer, heat is generated to 120 ℃ by self friction, and the materials are discharged (the materials are in a semi-molten state). Mixing the materials for 5min by a double-roll open mill with the roll moment of 4mm, performing thin-pass feeding for 3 times, cooling the materials into sheets, and cooling the sheets by cooling water through the double-roll open mill. And storing for 48 hours for later use to obtain the environment-friendly flame-retardant PVC/NBR foamed high-temperature adhesive sheet.
(2) Preparing the environment-friendly flame-retardant PVC/NBR foam material low-temperature adhesive:
weighing the environment-friendly flame-retardant PVC/NBR foam material high-temperature adhesive obtained in the step (1), a cross-linking agent, a composite accelerator, a composite foaming agent and a plasticizer (accounting for 29% of the total amount of the plasticizer). Pouring the mixture into an internal mixer in turn, internally mixing the mixture to 95 ℃, and discharging the mixture for later use. Then the mixture is milled by an open mill for 3min, the roller spacing is 8mm, the mixture is thinly passed for 3 times for blanking, and cooling water is introduced into the open mill. Obtaining the environment-friendly flame-retardant PVC/NBR foaming low-temperature adhesive sheet, and foaming and molding.
(3) Foaming and forming: and (5) foaming and forming by using an oven. Preheating an oven to 180 ℃, and then putting the environment-friendly flame-retardant PVC/NBR foaming low-temperature adhesive sheet obtained in the step (2) into the oven to heat for 15min to obtain the environment-friendly flame-retardant PVC/NBR foaming material.
Examples 2 to 6
The preparation method of the environment-friendly flame-retardant PVC/NBR foam material of each example is the same as that of example 1, except that the weight ratio of each component is shown in Table 1.
Table 1: example 1-6 formulation ratios
The environmental-friendly flame-retardant PVC/NBR foam materials prepared in the embodiments 1 to 6 are used for preparing a standard sample, and the flame retardant property, the mechanical property and the density of the standard sample are tested according to the national standard, and the test results are shown in the table 2.
Table 2: examples 1 to 6 set of recipes
| Testing performance | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Tensile strength/MPa | 0.88 | 0.90 | 0.78 | 0.83 | 0.79 | 0.92 |
| Elongation at break/% | 225 | 194 | 243 | 248 | 264 | 204 |
| Density/g.cm-3 | 0.215 | 0.234 | 0.203 | 0.203 | 0.195 | 0.294 |
| Oxygen index/% | 29.5 | 30.2 | 28.4 | 30.1 | 30.4 | 29.3 |
| Smoke Density (MSD) | 24.60 | 22.10 | 26.71 | 23.32 | 23.10 | 24.43 |
| Smoke Density (SDR) | 19.66 | 15.83 | 20.83 | 18.12 | 17.65 | 19.74 |
Comparative example
The preparation method of the environment-friendly flame-retardant PVC/NBR foam material of the comparative example is the same as that of the examples 1 and 2, except that calcium carbonate and DOP plasticizer are compared, and the details are shown in Table 3.
Table 3: formulation tables for examples and comparative examples
The prepared comparative example environment-friendly flame-retardant PVC/NBR foaming material is used for preparing a standard sample, and the flame retardant property, the mechanical property and the density of the standard sample are tested according to the national standard, and the test result is shown in Table 4.
Table 4: test results of environmentally friendly flame retardant PVC/NBR foam prepared in examples and comparative examples
| Testing performance | Example 1 | Example 2 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Tensile strength/MPa | 0.88 | 0.90 | 0.87 | 0.90 | 0.87 |
| Elongation at break/% | 225 | 194 | 232 | 214 | 230 |
| Density/g.cm-3 | 0.215 | 0.234 | 0.222 | 0.234 | 0.227 |
| Oxygen index/% | 29.5 | 30.2 | 24.6 | 24.8 | 22.6 |
| Smoke sealDegree (MSD) | 24.60 | 22.10 | 45.30 | 45.62 | 48.41 |
| Smoke Density (SDR) | 19.66 | 15.83 | 39.75 | 39.24 | 41.63 |
As can be seen from Table 4: as can be seen from comparison of examples 1 and 2 with comparative examples 1, 2 and 3, the invention adopts magnesium hydroxide and zinc borate as flame retardants, and can effectively improve the oxygen index and reduce the smoke density of the environment-friendly flame-retardant PVC/NBR foam material compared with calcium carbonate and DOP plasticizer.
Claims (9)
1. The environment-friendly flame-retardant foaming material is characterized by comprising the following components in parts by weight: 100 parts of PVC/NBR compound, 4-12 parts of composite foaming agent, 0.3-0.8 part of cross-linking agent, 1.8-2.5 parts of composite accelerator, 70-120 parts of composite halogen-free flame retardant, 25-40 parts of plasticizer, 2.0-4.0 parts of composite lubricant, 6-12 parts of reinforcing agent and 0.3-0.6 part of anti-aging agent;
the composite halogen-free flame retardant is prepared from active magnesium hydroxide and zinc borate according to the mass ratio of 10: 1-20: 1; the plasticizer is triphenyl phosphate or diphenyl isooctyl phosphate.
2. The foamed material according to claim 1, wherein the material consists of the following components in parts by weight: 100 parts of PVC/NBR compound, 10 parts of composite foaming agent, 0.5 part of cross-linking agent, 2.1 parts of composite accelerator, 100 parts of composite halogen-free flame retardant, 30 parts of plasticizer, 2.5 parts of composite lubricant, 8 parts of reinforcing agent and 0.4 part of anti-aging agent.
3. The foaming material of claim 2, wherein the PVC is emulsion polymerized PVC resin, and the PVC/NBR compound is composed according to a mass ratio of 1: 0.2-0.2: 1; the composite foaming agent comprises an AC foaming agent, an ACP-W foaming agent and zinc oxide according to the mass ratio of 12:1: 0.3-7: 1: 0.3; the cross-linking agent is sulfur; the composite lubricant is composed of stearic acid, solid paraffin and polyethylene glycol according to a mass ratio of 1:4: 2-1: 8: 4; the composite accelerator consists of DPTT, ZDBC, ZDEC and MBT according to the mass ratio of 2:2:2: 1; the reinforcing agent is carbon black, and the anti-aging agent is anti-aging agent RD or anti-aging agent DNP.
4. The foamed material according to claim 3, wherein the PVC/NBR formulation is comprised in a mass ratio of 1: 1.
5. The foamed material according to claim 3, wherein the composite foaming agent is prepared from an AC foaming agent: ACP-W foaming agent: the zinc oxide is composed according to the mass ratio of 8.7:1: 0.3.
6. The foamed material according to claim 3, wherein the composite lubricant is stearic acid: solid paraffin: the polyethylene glycol is prepared according to the mass ratio of 1:4: 2.
7. The foam material of claim 3, wherein the composite halogen-free flame retardant is active magnesium hydroxide: the zinc borate is prepared according to the mass ratio of 15: 1.
8. The process for the preparation of expanded materials according to any one of claims 1 to 7, characterized in that it comprises the following steps:
(1) preparing PVC/NBR foam material high-temperature glue: weighing a composite foaming agent, a composite halogen-free flame retardant, a reinforcing agent, a composite lubricant, an anti-aging agent, a plasticizer and PVC resin according to a formula, sequentially feeding the materials into an internal mixer, wherein the rotating speed of a rotor of the internal mixer is 50n/min, the materials are internally mixed in the internal mixer, the materials are subjected to heat generation to 120 ℃ by means of self friction, discharging is carried out, the materials are mixed for 3-5 min by a double-roll open mill, the roll moment is 3-4 mm, the materials are subjected to thin passing for 3-4 times for blanking and are cooled into sheets, the double-roll open mill is cooled by cooling water, and the sheets are stored for 24-48 hours for later;
(2) preparing the PVC/NBR foam material low-temperature adhesive:
weighing the environment-friendly flame-retardant PVC/NBR foaming material high-temperature adhesive obtained in the step (1), a crosslinking agent, a composite accelerator, a composite foaming agent and a plasticizer, pouring the materials into an internal mixer, carrying out internal mixing to 90-95 ℃ for about 5-6min, discharging for later use, carrying out open milling by using an open mill for 2-3 min, carrying out roll spacing of 7-9 mm, carrying out thin-passing for 3-4 times, and introducing cooling water into the open mill to obtain a PVC/NBR foaming low-temperature adhesive sheet;
(3) foaming and forming: and (3) performing foaming molding by using an oven, preheating the oven to 160-180 ℃, and then putting the PVC/NBR foamed low-temperature rubber sheet obtained in the step (2) into the oven to heat for 13-18 min to obtain the PVC/NBR foamed material.
9. Use of the foamed material according to any one of claims 1 to 7 in the fields of interior fire-proof decorative materials, sound-and heat-insulating materials, and air-conditioning copper pipe heat-insulating materials.
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| CN111732857A (en) * | 2020-07-09 | 2020-10-02 | 浙江善力高科新材料有限公司 | SEFoamtex material formula |
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| CN1241593A (en) * | 1998-12-31 | 2000-01-19 | 宜兴市凯凯橡塑保温材料厂 | Rubber-plastic sponge heat-insulating fireproof material and its production process |
| KR20130060440A (en) * | 2011-11-30 | 2013-06-10 | (주)하이코리아 | Laminated rubber foam adiabatic material and manufacturing method thereof |
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