Special material for high-flame-retardant temperature-resistant polyvinyl chloride foam material and preparation method thereof
By using combined materials such as polyphenylene sulfide fiber and polyamide resin in polyvinyl chloride foam materials, the formulation and preparation process are optimized, and the shortcomings of traditional PVC foam materials in flame retardancy and temperature resistance are solved, and high resistance is achieved The improvement of combustion temperature resistance and cost reduction have broadened the scope of application.
Patent Information
- Application Number
- CN202411470236.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-21
- Publication Date
- 2024-12-17
AI Technical Summary
Traditional polyvinyl chloride (PVC) foam materials have shortcomings in flame retardancy and temperature resistance. The existing flame retardants increase costs and are toxic. Organophosphorus flame retardants volatilize and produce irritating odors. The poor high temperature resistance performance leads to extremes. Soften or burn under working conditions, affecting the application range.
Using a combination of polyphenylene sulfide fiber, polyamide resin, chain extender, nucleating agent, foaming agent and processing auxiliary agent, the high flame retardant and temperature-resistant polyvinyl chloride foam material is prepared by optimizing the material formulation and preparation process to ensure that The material improves temperature resistance while maintaining toughness and flame retardant properties.
It achieves the significant improvement of temperature resistance while ensuring flame retardant performance, reduce production costs, and broaden the application range of materials, avoiding the problems of cost increase and performance decline in traditional methods.
Smart Images
Figure BDA0005094489620000081
Abstract
Description
Technical Field
[0001] The invention relates to the field of polymer materials, and in particular to a highly flame-retardant and heat-resistant polyvinyl chloride foam material and a preparation method thereof. Background Art
[0002] Polyvinyl chloride (PVC) foam materials, as an important component of the polymer material field, have been widely used in many industries such as construction, automobiles, and packaging due to their light weight, corrosion resistance, and good processing performance. However, with the advancement of technology and the enhancement of environmental awareness, the challenges faced by traditional PVC foam materials in terms of flame retardancy, temperature resistance, and environmental protection are becoming increasingly prominent.
[0003] In terms of flame retardancy, although there are many PVC foam materials with flame retardant function on the market, their actual effects are often uneven. Publication No. CN113563677A discloses a flame retardant PVC foam and a preparation method thereof, which is composed of PVC resin, plasticizer, crosslinking agent, foaming agent, epoxy compound, antioxidant, tris(β-chloroisopropyl) phosphate, ammonium molybdate and flame retardant masterbatch; in parts by weight, the flame retardant masterbatch is a composition of 5-8 parts of polyvinyl chloride resin, 15-20 parts of magnesium hydroxide, 35-40 parts of diphenylcresyl phosphate, 30-35 parts of dimethyl aluminum hypophosphite and 13-15 parts of aluminum hydroxide. It improves the flame retardant grade of the material by adding an organic phosphorus flame retardant, but this practice not only increases the cost, but also the organic phosphorus compounds, cationic surfactants and other components contained in the organic phosphorus flame retardant are easily volatilized during the processing process, which will cause irritating odors and toxic gases to be generated, and dripping is generated during combustion, posing a threat to the environment and human health.
[0004] In terms of high temperature resistance, traditional PVC foam materials are prone to softening, deformation and even burning in high temperature environments, limiting their application in some extreme working conditions. The invention patent with publication number CN201910540574 discloses a special material for PVC heat-resistant foam products. Styrene-cinnamic acid-acrylonitrile terpolymer is used as a heat-resistant modifier in the formula to improve the heat resistance of PVC. Due to the significant differences in the molecular structure of styrene-cinnamic acid-acrylonitrile terpolymer, this may lead to poor compatibility when mixed, resulting in phase separation, stratification or performance degradation during processing and use, affecting the quality and stability of the final product. At the same time, 520 parts of heat-resistant modifier are required for every 100 parts of PVC, which greatly increases the formulation cost.
[0005] The heat resistance of PVC foam can be improved by introducing high temperature resistant resin or nano filler, but these methods are often accompanied by the problem of reduced material toughness or sharply increased cost. The present invention optimizes the material formula and preparation process to achieve the PVC foam material while maintaining good toughness and significantly improving its heat resistance, thereby broadening the application range of the material. Summary of the invention
[0006] In order to solve the above problems, the present invention provides a special material for highly flame-retardant and heat-resistant polyvinyl chloride foam material. The highly flame-retardant and heat-resistant polyvinyl chloride foam material produced by the present invention can overcome the defects of the existing PVC foam products in the background technology that the flame retardancy and heat resistance cannot be taken into account at the same time.
[0007] The present invention is achieved through the following technical solutions:
[0008] A special material for highly flame-retardant and heat-resistant polyvinyl chloride foam material, comprising the following components in parts by weight: the special material for highly flame-retardant and heat-insulating polyvinyl chloride foam material comprises the following components in parts by weight: 100 parts of polyvinyl chloride resin, 2-5 parts of polyphenylene sulfide fiber, 3-15 parts of polyamide resin, 6-10 parts of chain extender, 5-15 parts of foaming agent, 25-35 parts of nucleating agent, 1-3 parts of compatibilizer, and 4-6 parts of processing aid;
[0009] The relative molecular weight of the polyvinyl chloride resin is in the range of 60,000 to 150,000;
[0010] The nucleating agent is one or more of calcium carbonate, montmorillonite, kaolin, talc, calcium silicate, magnesium hydroxide, aluminum hydroxide, and white carbon black;
[0011] The processing aid includes one or more of a heat stabilizer, a flame retardant, an antioxidant, and a colorant;
[0012] The polyamide resin is one or more of PA6 and PA66.
[0013] The preferred polyphenylene sulfide fiber has a weight average molecular weight of 49000-51000, a fineness of 4.5-6.5 dtex, and a length of ≤2 mm.
[0014] Preferred chain extenders are diisocyanate chain extenders or diamine chain extenders.
[0015] The preferred chain extender is a diisocyanate chain extender, including one or more of methylene diphenyl diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, methylene dicyclohexyl diisocyanate, isophorone diisocyanate, and cyclohexane dimethyl diisocyanate.
[0016] Preferred diamine chain extenders are aliphatic diamine chain extenders, including one or more of 3,5-dimethylthiotoluenediamine, diethyltoluenediamine, 1,3-propylene glycol bis(4-aminobenzoate), 4,4'-methylenebis(2-ethyl)aniline, and bis-sec-butylaminodiphenylmethane.
[0017] The preferred foaming agent is a combination of two or three of azobisisobutyronitrile, azodicarbonamide, N,N-dinitrosopentamethylenetetramine, urea and sodium bicarbonate.
[0018] As a further improvement of the above, 1-10 parts by weight of hollow glass microspheres are added to the composition, the particle size of the hollow glass microspheres is in the range of 25-95 μm, and the true density is 0.15-0.25 g / cm 3 , softening temperature is less than or equal to 600℃.
[0019] The present invention provides a method for preparing a special material for highly flame-retardant and heat-resistant polyvinyl chloride foam material, which is characterized by comprising the steps in the following order:
[0020] The first step is to weigh all the components except the foaming agent component according to the components and weight parts, and knead them in a kneading machine at a high speed for 5-10 minutes at a kneading temperature of 100-130°C;
[0021] The second step is to put the kneaded materials into a low-speed mixer and quickly cool them for 5-10 minutes until the material temperature drops to 25-30°C;
[0022] The third step is to add the foaming agent in a low-speed mixer, and continue to mix at a low speed for 10-20 minutes to obtain the special material for highly flame-retardant and heat-resistant polyvinyl chloride foam material.
[0023] Compared with the prior art, the present invention has the following beneficial effects:
[0024] The special material formula of the highly flame-retardant and heat-resistant polyvinyl chloride foam material of the present invention adopts polyphenylene sulfide fiber as a flame-retardant and high-temperature resistant auxiliary agent, and is mixed with other auxiliary agents and polyvinyl chloride resin to obtain a special material. The polyvinyl chloride foam material produced by the special material utilizes the synergistic effect of flame retardancy and high-temperature resistance, and while ensuring the flame retardant performance, the high-temperature resistance performance is also improved. The production cost is low, the application range is wide, and the market prospect is very large. DETAILED DESCRIPTION
[0025] The present invention is further described below with reference to examples. The raw materials used in the examples are all commercially available, and the following parts are parts by weight. Example 1
[0026] 100 parts of PVC resin, 2 parts of polyphenylene sulfide fiber, 3 parts of PA66, 6 parts of TDI (toluene diisocyanate), 4 parts of azobisisobutyronitrile, 1 part of azodicarbonamide, 25 parts of calcium carbonate, 1 part of phthalic anhydride, 2 parts of calcium zinc stabilizer, 1 part of antimony pentoxide, and 1 part of antioxidant 1010 are mixed to obtain a PVC foaming material; then the PVC foaming material and the solvent are measured in a weight ratio of 1:0.5 and mixed at a pressure of 10 MPa, and then injected into a closed mold cavity, heated to 160°C, maintained for 15 minutes, quickly cooled to 30°C, and then opened the mold, demolded, and post-ripened for 1 day to obtain a PVC highly flame-retardant and heat-resistant foam material. Comparative Example 1
[0027] 100 parts of PVC resin (paste resin), 15 parts of styrene-cinnamic acid-acrylonitrile terpolymer, 4.8 parts of calcium zinc stabilizer, 0.4 parts of polyethylene wax, 0.2 parts of stearic acid, 1.1 parts of methyl methacrylate and acrylate copolymer, 3.9 parts of azodicarbonamide, 13 parts of calcium carbonate, 3 parts of styrene and methyl methacrylate random copolymer are mixed at high and low temperatures to form a special material, and the special material is extruded, cooled and set, and cut to a fixed length to obtain a highly flame-retardant and heat-resistant polyvinyl chloride foam material.
[0028] The process parameters of extrusion molding are as follows: the barrel temperature includes four temperature intervals of 150°C, 165°C, 180°C and 175°C, the die lip temperature is 75°C, the setting table temperature is 30°C, the main engine speed of the extruder is 8.0rpm, and the pulling speed during melt extrusion is 2.25m / min.
[0029] The density of the foamed material prepared in Comparative Example 1 is 0.62 g / cm 3 , Vicat softening temperature 86.3℃, oxygen index 26%. Example 2
[0030] 100 parts of PVC resin, 5 parts of polyphenylene sulfide fiber, 10 parts of PA6, 8 parts of MDI (methylene diphenyl diisocyanate), 7.5 parts of foaming agent H, 5 parts of urea, 2 parts of hollow glass microspheres, 30 parts of talc, 3 parts of maleic anhydride, 2 parts of phosphite stabilizer, 2 parts of zinc borate, and 2 parts of antioxidant 1076 are mixed to obtain a PVC foaming material; then the PVC foaming material and the solvent are measured in a weight ratio of 1:0.5 and mixed at a pressure of 15 MPa, and then injected into a closed mold cavity, heated to 170°C, maintained for 10 minutes, quickly cooled to 20°C, and then opened the mold, demolded, and post-ripened for 1 day to obtain a PVC highly flame-retardant and heat-resistant foam material. Example 3
[0031] 100 parts of PVC resin, 2 parts of polyphenylene sulfide fiber, 15 parts of PA6, 6 parts of XDI (xylylene diisocyanate), 7 parts of azobisisobutyronitrile, 3 parts of foaming agent H, 2 parts of urea, 5 parts of hollow glass microspheres, 35 parts of calcium silicate, 1.5 parts of 3,3',4,4'-diphenyl ether tetraanhydride, 2 parts of dibutyltin dilaurate, 1.5 parts of antimony pentoxide, and 1.5 parts of antioxidant 168 are mixed to obtain a PVC foaming material; then the PVC foaming material and the solvent are measured in a weight ratio of 1:0.5, mixed at a pressure of 20 MPa, and injected into a closed mold cavity, heated to 180°C, maintained for 5 minutes, quickly cooled to 25°C, and then opened, demolded, and post-cured for 1 day to obtain a highly flame-retardant and heat-resistant polyvinyl chloride foam material. Example 4
[0032] 100 parts of PVC resin, 3 parts of polyphenylene sulfide fiber, 7.5 parts of PA6, 7.5 parts of PA66, 7 parts of PPDI (p-phenylene diisocyanate), 3 parts of azobisisobutyronitrile, 7 parts of N,N'-dinitrosopentamethylenetetramine, 4.5 parts of urea, 10 parts of hollow glass microspheres, 25 parts of magnesium hydroxide, 3 parts of 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3 parts of epoxy soybean oil, 1 part of red phosphorus, and 1 part of antioxidant 1010 are mixed to obtain a special material for PVC foaming; then the PVC slurry and the solvent are measured in a weight ratio of 1:0.5 and mixed at a pressure of 16 MPa and injected into a closed mold cavity, the temperature is raised to 175°C, maintained for 8 minutes, and the temperature is quickly lowered to 25°C before opening the mold, demolding, and post-aging for 1 day to obtain a highly flame-retardant and heat-resistant polyvinyl chloride foam material. Example 5
[0033] 100 parts of PVC resin, 4 parts of polyphenylene sulfide fiber, 10 parts of PA6, 5 parts of PA66, 10 parts of 3,5-dimethylthiotoluenediamine, 2 parts of azobisisobutyronitrile, 8 parts of N,N'-dinitrosopentamethylenetetramine, 5 parts of urea, 5 parts of hollow glass microspheres, 30 parts of white carbon black, 2 parts of dibutyltin dilaurate, 1 part of antimony pentoxide, and 1 part of antioxidant 1010 are mixed to obtain PVC slurry; then the PVC slurry and the solvent are measured in a weight ratio of 1:0.5 and mixed at a pressure of 18 MPa, and then injected into a closed mold cavity, heated to 170°C, maintained for 10 minutes, quickly cooled to 20°C, and then the mold is opened, demolded, and post-ripened for 1 day to obtain a highly flame-retardant and heat-resistant polyvinyl chloride foam material. Example 6
[0034] 100 parts of PVC resin, 4 parts of polyphenylene sulfide fiber, 5 parts of PA6, 10 parts of PA66, 7.5 parts of diethyltoluenediamine, 8 parts of azobisisobutyronitrile, 2 parts of sodium bicarbonate, 8 parts of hollow glass microspheres, 35 parts of aluminum hydroxide, 3 parts of phthalic anhydride, 2 parts of tris(trimethylsilyl)phosphite stabilizer, 3 parts of antimony pentoxide, and 0.5 parts of antioxidant 1076 are mixed to obtain a PVC foaming material; then the PVC foaming material and the solvent are measured in a weight ratio of 1:0.5, mixed at a pressure of 19 MPa, and injected into a closed mold cavity, heated to 172°C, maintained for 10 minutes, quickly cooled to 24°C, and then opened the mold, demolded, and post-ripened for 1 day to obtain a highly flame-retardant and heat-resistant polyvinyl chloride foam material. Example 7
[0035] 100 parts of PVC resin, 5 parts of polyphenylene sulfide fiber, 15 parts of PA66, 7 parts of 4,4'-methylenebis(2-ethyl)aniline, 7 parts of azobisisobutyronitrile, 5 parts of azodicarbonamide, 0.5 parts of sodium bicarbonate, 10 parts of hollow glass microspheres, 20 parts of calcium carbonate, 10 parts of talcum powder, 3 parts of triphenyl phosphite stabilizer, 2 parts of antimony pentoxide, and 1 part of antioxidant 168 are mixed to obtain a PVC foaming material; then the PVC foaming material and the solvent are measured in a weight ratio of 1:0.5, mixed at a pressure of 13 MPa, and injected into a closed mold cavity, heated to 165°C, maintained for 10 minutes, quickly cooled to 22°C, and then opened the mold, demolded, and post-ripened for 1 day to obtain a highly flame-retardant and heat-resistant polyvinyl chloride foam material. Example 8
[0036] 100 parts of PVC resin, 3 parts of polyphenylene sulfide fiber, 15 parts of PA6, 8 parts of 1,3-propylene glycol bis(4-aminobenzoate), 8 parts of foaming agent H, 5 parts of urea, 5 parts of hollow glass microspheres, 15 parts of magnesium hydroxide, 15 parts of aluminum hydroxide, 2 parts of calcium zinc stabilizer, and 1.5 parts of antimony pentoxide are mixed to obtain a PVC foaming material; then the PVC foaming material and the solvent are measured in a weight ratio of 1:0.5, mixed at a pressure of 14 MPa, and injected into a closed mold cavity, heated to 170°C, maintained for 10 minutes, quickly cooled to 23°C, and then opened the mold, demolded, and post-cured for 1 day to obtain a highly flame-retardant and heat-resistant polyvinyl chloride foam material.
[0037] Performance data sheet
Claims
1. A highly flame-retardant and heat-resistant polyvinyl chloride foam material, characterized in that: The special material for highly flame-retardant and heat-insulating polyvinyl chloride foam material comprises the following components in parts by weight: 100 parts of polyvinyl chloride resin, 2-5 parts of polyphenylene sulfide fiber, 3-15 parts of polyamide resin, 6-10 parts of chain extender, 5-15 parts of foaming agent, 25-35 parts of nucleating agent, 1-3 parts of compatibilizer, and 4-6 parts of processing aid; The relative molecular weight of the polyvinyl chloride resin is in the range of 60,000 to 150,000; The nucleating agent is one or more of calcium carbonate, montmorillonite, kaolin, talc, calcium silicate, magnesium hydroxide, aluminum hydroxide, and white carbon black; The processing aid includes one or more of a heat stabilizer, a flame retardant, an antioxidant, and a colorant; The polyamide resin is one or more of PA6 and PA66.
2. The highly flame-retardant and heat-resistant polyvinyl chloride foam material according to claim 1, characterized in that The polyphenylene sulfide fiber has a weight average molecular weight of 49000-51000, a fineness of 4.5-6.5 dtex, and a length of less than or equal to 2 mm.
3. The highly flame-retardant and heat-resistant polyvinyl chloride foam material according to claim 1 is characterized in that The chain extender is a diisocyanate chain extender or a diamine chain extender.
4. The highly flame-retardant and heat-resistant polyvinyl chloride foam material according to claim 3 is characterized in that The diisocyanate chain extender includes one or more of methylene diphenyl diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, methylene dicyclohexyl diisocyanate, isophorone diisocyanate and cyclohexane dimethyl diisocyanate.
5. The highly flame-retardant and heat-resistant polyvinyl chloride foam material according to claim 3 is characterized in that The diamine chain extender is an aliphatic diamine chain extender, and the aliphatic diamine chain extender includes one or more of 3,5-dimethylthiotoluenediamine, diethyltoluenediamine, 1,3-propylene glycol bis(4-aminobenzoate), 4,4'-methylenebis(2-ethyl)aniline, and di-sec-butylaminodiphenylmethane.
6. The highly flame-retardant and heat-resistant polyvinyl chloride foam material according to claim 1, characterized in that The foaming agent is a combination of two or three of azobisisobutyronitrile, azodicarbonamide, N,N'-dinitrosopentamethylenetetramine, urea and sodium bicarbonate.
7. The highly flame-retardant and heat-resistant polyvinyl chloride foam material according to claim 1 is characterized in that The compatibilizer is a dibasic acid anhydride, including one or more of phthalic anhydride, maleic anhydride, 3,3',4,4'-diphenyl ether tetraanhydride, and 3,3',4,4'-biphenyl tetracarboxyl dianhydride.
8. The highly flame-retardant and heat-resistant polyvinyl chloride foam material according to any one of claims 1 to 7, characterized in that Also included are hollow glass microspheres in an amount of 1-10 parts by weight, hollow glass microspheres having a particle size range of 25-95 μm and a true density of 0.15-0.25 g / cm 3 , softening temperature is less than or equal to 600℃.
9. The method for preparing any one of the highly flame-retardant and heat-resistant polyvinyl chloride foam material special materials according to claims 1-8, characterized in that: The steps include the following order: The first step is to weigh all the components except the foaming agent component according to the components and weight parts, and knead them in a kneading machine at a high speed for 5-10 minutes at a kneading temperature of 100-130°C; The second step is to put the kneaded materials into a low-speed mixer and quickly cool them for 5-10 minutes until the material temperature drops to 25-30°C; The third step is to add the foaming agent in a low-speed mixer, and continue to mix at a low speed for 10-20 minutes to obtain the special material for highly flame-retardant and heat-resistant polyvinyl chloride foam material.