CN109851946B - Flame-retardant and aging-resistant plastic shell - Google Patents
Flame-retardant and aging-resistant plastic shell Download PDFInfo
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Abstract
The invention relates to the technical field of plastic shells, in particular to a flame-retardant and aging-resistant plastic shell which is prepared from the raw materials of PVC, a plasticizer, a heat stabilizer, a flame retardant, a flexibilizer, an antioxidant and a lubricant, wherein the flexibilizer is mainly prepared from castor oil, 2, 4-toluene diisocyanate and nano silicon dioxide. According to the invention, the flame retardant, the heat stabilizer and the antioxidant are added into PVC, so that the PVC composite material has better flame retardance and aging resistance, and in order to improve the impact resistance of PVC, the castor oil polyurethane is adopted to coat the nano silicon dioxide to prepare the toughening agent, and the coating treatment improves the dispersibility of the nano silicon dioxide in the PVC, so that the toughening effect is better, and meanwhile, the castor oil polyurethane also has better elasticity, so that the toughening agent synergistically enhances the toughness of the PVC through two completely different mechanisms of elastomer toughening and rigid toughening, so that the PVC has excellent impact resistance, and the performance requirement of a plug shell is met.
Description
Technical Field
The invention relates to the technical field of plastic shells, in particular to a flame-retardant and anti-aging plastic shell.
Background
The plug is a key component of a power line connected with strong electricity, so the quality of the performance of the plug directly influences the safe use, wherein the plug of the power line is easy to generate heat in the working process of a high-power occasion or generates an ignition phenomenon when carrying instant high voltage, and the heat or spark can be the origin of fire to cause combustion and must be paid attention to.
Polyvinyl chloride (PVC) is widely used for injection molding of various power line plugs due to good physical and mechanical properties, excellent electrical insulation, simple injection molding process and low price, and PVC materials used for plug materials mainly comprise PVC resin, a plasticizer, a heat stabilizer, a flame retardant, an impact modifier and the like.
However, PVC has poor impact resistance and is deficient in flame retardance and aging resistance.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a flame-retardant and aging-resistant plastic shell.
The purpose of the invention is realized by the following technical scheme:
the flame-retardant and aging-resistant plastic shell comprises the following raw materials in parts by weight:
the preparation method of the toughening agent comprises the following steps:
(1) alcoholysis: carrying out alcoholysis reaction on castor oil and glycerol under the catalysis of a catalyst, wherein the reaction temperature is 200-220 ℃, and the reaction time is 1.5-2.5h, so as to obtain alcoholysis castor oil, and the castor oil, the glycerol and the catalyst are prepared according to the weight ratio of 500:80-120: 1-3;
(2) modification: dissolving 2, 4-toluene diisocyanate in N, N-dimethylacetamide, adding nano silicon dioxide, stirring and mixing to obtain an isocyanate solution, wherein the weight ratio of the 2, 4-toluene diisocyanate to the nano silicon dioxide to the N, N-dimethylacetamide is 5-7:1-2: 10;
(3) and (3) polyurethane synthesis: adding the alcoholysis castor oil into an isocyanate solution for reaction at the temperature of 50-70 ℃ for 2-3h to obtain a polyurethane prepolymer solution, wherein the weight ratio of the alcoholysis castor oil to the isocyanate solution is 1: 2-4;
(4) spraying: and (3) carrying out electrostatic spraying on the polyurethane prepolymer solution to obtain the toughening agent.
The flame retardant, the heat stabilizer and the antioxidant are added into the PVC, so that the PVC composite material meets the flame retardance and the aging resistance required by plugs, and the special toughening agent is added to improve the impact resistance of the PVC. In the prior art, impact modifiers suitable for PVC are generally CPE, ACR, MBS and the like, and the impact modifiers have advantages and disadvantages, but the existing impact modifiers mainly depend on import and have higher cost, and the requirement on dispersibility is high if the rigid toughening particles with lower cost need to play a better toughening effect. According to the invention, the castor oil polyurethane is adopted to coat the nano silicon dioxide to prepare the toughening agent, the coating treatment improves the dispersibility of the nano silicon dioxide in PVC, so that the toughening effect is good, and meanwhile, the castor oil polyurethane also has good elasticity, so that the toughening agent synergistically enhances the toughness of PVC through two completely different mechanisms of elastomer toughening and rigidity toughening, so that the PVC has excellent impact resistance, and the performance requirements of a plug shell are met.
Wherein the catalyst is triethanolamine. The triethanolamine serving as a reaction type catalyst can improve the alcoholysis efficiency of the castor oil, change the molecular structure of the castor oil and improve the toughness of the prepared polyurethane.
Wherein the particle size of the nano silicon dioxide is 100-200nm, and the particle size of the toughening agent is 26.3-41.5 mu m. According to the invention, the nano-silica is coated by adopting polyurethane, so that the problem of easy agglomeration of the nano-silica can be solved by adopting the nano-diameter silica, and the self-agglomeration of the silica in the spraying process can be avoided, so that the particle size is preferably 100-200nm, and the particle size of the toughening agent is also controlled by controlling the particle size of the nano-silica, so that the prepared micron-sized toughening agent can have better dispersibility in PVC, and has a remarkable toughening effect.
Wherein the plasticizer is at least one of trioctyl trimellitate, dioctyl adipate and dioctyl sebacate. The plasticizer has the function of improving the processing fluidity of PVC, and is beneficial to mixing and dispersing of various materials.
Wherein the plasticizer consists of trioctyl trimellitate, dioctyl adipate and dioctyl sebacate in a weight ratio of 1-2:1-2: 1. The plasticizer selected by compounding is remarkable in improvement of the processability of PVC, and is beneficial to uniform distribution of various additives such as a toughening agent and a heat stabilizer in PVC, and the plastic shell is not easy to locally age and has higher stability.
Wherein the heat stabilizer is a calcium-zinc composite heat stabilizer.
Wherein the flame retardant consists of ammonium polyphosphate, triphenyl phosphate and aluminum hydroxide according to the weight ratio of 1-3:1-2: 0.4-0.6. When the mechanical property of the plastic shell is not influenced as much as possible, the flame retardant selected by compounding can enable the flame retardance of the plastic shell to reach the V0 level and improve the thermal stability of the plastic shell.
Wherein the antioxidant consists of an antioxidant 168 and an antioxidant 1010 according to the weight ratio of 1: 1.
Wherein the lubricant is at least one of talcum powder, calcium stearate and polyethylene wax. The lubricant can improve the melt fluidity and the demolding property, is beneficial to the uniform distribution of various additives such as a toughening agent, a heat stabilizer and the like in PVC, and reduces the processing difficulty.
The flame-retardant and aging-resistant plastic shell is prepared by the following method: weighing the raw materials in parts by weight, dispersing and mixing, then carrying out melt extrusion granulation, and carrying out injection molding to obtain the flame-retardant and aging-resistant plastic shell.
The invention has the beneficial effects that: according to the invention, the flame retardant, the heat stabilizer and the antioxidant are added into PVC, so that the PVC composite material meets the flame retardance and the aging resistance required by a plug, and in order to improve the impact resistance of PVC, castor oil polyurethane is adopted to coat nano silicon dioxide to prepare the toughening agent, and the coating treatment improves the dispersibility of the nano silicon dioxide in PVC, so that the toughening effect is better, and meanwhile, the castor oil polyurethane also has better elasticity, so that the toughening agent synergistically enhances the toughness of PVC through two completely different mechanisms of elastomer toughening and rigid toughening, so that the PVC has excellent impact resistance, and meets the performance requirements of a plug shell.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
The flame-retardant and aging-resistant plastic shell comprises the following raw materials in parts by weight:
the preparation method of the toughening agent comprises the following steps:
(1) alcoholysis: carrying out alcoholysis reaction on castor oil and glycerol under the catalysis of a catalyst, wherein the reaction temperature is 210 ℃, the reaction time is 2 hours, and the alcoholysis castor oil is obtained, and the castor oil, the glycerol and the catalyst are prepared according to the weight ratio of 500:100: 2;
(2) modification: dissolving 2, 4-toluene diisocyanate in N, N-dimethylacetamide, adding nano silicon dioxide, stirring and mixing to obtain an isocyanate solution, wherein the weight ratio of the 2, 4-toluene diisocyanate to the nano silicon dioxide to the N, N-dimethylacetamide is 6:1.5: 10;
(3) and (3) polyurethane synthesis: adding the alcoholysis castor oil into an isocyanate solution for reaction at the temperature of 60 ℃ for 2.5 hours to obtain a polyurethane prepolymer solution, wherein the weight ratio of the alcoholysis castor oil to the isocyanate solution is 1: 3;
(4) spraying: and (3) carrying out electrostatic spraying on the polyurethane prepolymer solution to obtain the toughening agent.
Wherein the catalyst is triethanolamine.
Wherein the particle size of the nano silicon dioxide is 150nm, and the particle size of the toughening agent is 34.1 mu m.
The plasticizer is composed of trioctyl trimellitate, dioctyl adipate and dioctyl sebacate in a weight ratio of 1.5:1.5: 1.
Wherein the heat stabilizer is a calcium-zinc composite heat stabilizer.
The flame retardant consists of ammonium polyphosphate, triphenyl phosphate and aluminum hydroxide according to the weight ratio of 2:1.5: 0.5.
Wherein the antioxidant consists of an antioxidant 168 and an antioxidant 1010 according to the weight ratio of 1: 1.
Wherein the lubricant is composed of talcum powder, calcium stearate and polyethylene wax according to the weight ratio of 1:1: 2.
The flame-retardant and aging-resistant plastic shell is prepared by the following method: weighing the raw materials in parts by weight, dispersing and mixing, then carrying out melt extrusion granulation, and carrying out injection molding to obtain the flame-retardant and aging-resistant plastic shell.
Example 2
The flame-retardant and aging-resistant plastic shell comprises the following raw materials in parts by weight:
the preparation method of the toughening agent comprises the following steps:
(1) alcoholysis: carrying out alcoholysis reaction on castor oil and glycerol under the catalysis of a catalyst, wherein the reaction temperature is 200 ℃, the reaction time is 1.5 hours, and alcoholysis castor oil is obtained, and the castor oil, the glycerol and the catalyst are prepared according to the weight ratio of 500:80: 1;
(2) modification: dissolving 2, 4-toluene diisocyanate in N, N-dimethylacetamide, adding nano silicon dioxide, stirring and mixing to obtain an isocyanate solution, wherein the weight ratio of the 2, 4-toluene diisocyanate to the nano silicon dioxide to the N, N-dimethylacetamide is 5:1: 10;
(3) and (3) polyurethane synthesis: adding the alcoholysis castor oil into an isocyanate solution for reaction at 50 ℃ for 2 hours to obtain a polyurethane prepolymer solution, wherein the weight ratio of the alcoholysis castor oil to the isocyanate solution is 1: 2;
(4) spraying: and (3) carrying out electrostatic spraying on the polyurethane prepolymer solution to obtain the toughening agent.
Wherein the catalyst is triethanolamine.
Wherein the particle size of the nano silicon dioxide is 100nm, and the particle size of the toughening agent is 26.3 mu m.
The plasticizer is composed of trioctyl trimellitate, dioctyl adipate and dioctyl sebacate in a weight ratio of 1:1: 1.
Wherein the heat stabilizer is a calcium-zinc composite heat stabilizer.
The flame retardant consists of ammonium polyphosphate, triphenyl phosphate and aluminum hydroxide according to the weight ratio of 1:1: 0.4.
Wherein the antioxidant consists of an antioxidant 168 and an antioxidant 1010 according to the weight ratio of 1: 1.
Wherein the lubricant is talcum powder.
The flame-retardant and aging-resistant plastic shell is prepared by the following method: weighing the raw materials in parts by weight, dispersing and mixing, then carrying out melt extrusion granulation, and carrying out injection molding to obtain the flame-retardant and aging-resistant plastic shell.
Example 3
The flame-retardant and aging-resistant plastic shell comprises the following raw materials in parts by weight:
the preparation method of the toughening agent comprises the following steps:
(1) alcoholysis: carrying out alcoholysis reaction on castor oil and glycerol under the catalysis of a catalyst, wherein the reaction temperature is 220 ℃, the reaction time is 2.5 hours, and alcoholysis castor oil is obtained, and the castor oil, the glycerol and the catalyst are prepared according to the weight ratio of 500:120: 3;
(2) modification: dissolving 2, 4-toluene diisocyanate in N, N-dimethylacetamide, adding nano silicon dioxide, stirring and mixing to obtain an isocyanate solution, wherein the weight ratio of the 2, 4-toluene diisocyanate to the nano silicon dioxide to the N, N-dimethylacetamide is 7:2: 10;
(3) and (3) polyurethane synthesis: adding the alcoholysis castor oil into an isocyanate solution for reaction at 70 ℃ for 3 hours to obtain a polyurethane prepolymer solution, wherein the weight ratio of the alcoholysis castor oil to the isocyanate solution is 1: 4;
(4) spraying: and (3) carrying out electrostatic spraying on the polyurethane prepolymer solution to obtain the toughening agent.
Wherein the catalyst is triethanolamine.
Wherein the particle size of the nano silicon dioxide is 200nm, and the particle size of the toughening agent is 41.5 mu m.
The plasticizer is composed of trioctyl trimellitate, dioctyl adipate and dioctyl sebacate according to the weight ratio of 2:2: 1.
Wherein the heat stabilizer is a calcium-zinc composite heat stabilizer.
The flame retardant consists of ammonium polyphosphate, triphenyl phosphate and aluminum hydroxide according to the weight ratio of 3:2: 0.6.
Wherein the antioxidant consists of an antioxidant 168 and an antioxidant 1010 according to the weight ratio of 1: 1.
Wherein the lubricant is polyethylene wax.
The flame-retardant and aging-resistant plastic shell is prepared by the following method: weighing the raw materials in parts by weight, dispersing and mixing, then carrying out melt extrusion granulation, and carrying out injection molding to obtain the flame-retardant and aging-resistant plastic shell.
Example 4
The flame-retardant and aging-resistant plastic shell comprises the following raw materials in parts by weight:
the preparation method of the toughening agent comprises the following steps:
(1) alcoholysis: carrying out alcoholysis reaction on castor oil and glycerol under the catalysis of a catalyst, wherein the reaction temperature is 205 ℃, the reaction time is 1.8h, and alcoholysis castor oil is obtained, and the castor oil, the glycerol and the catalyst are prepared according to the weight ratio of 500:90: 1.5;
(2) modification: dissolving 2, 4-toluene diisocyanate in N, N-dimethylacetamide, adding nano silicon dioxide, stirring and mixing to obtain an isocyanate solution, wherein the weight ratio of the 2, 4-toluene diisocyanate to the nano silicon dioxide to the N, N-dimethylacetamide is 6:1: 10;
(3) and (3) polyurethane synthesis: adding the alcoholysis castor oil into an isocyanate solution for reaction at the temperature of 55 ℃ for 2.2 hours to obtain a polyurethane prepolymer solution, wherein the weight ratio of the alcoholysis castor oil to the isocyanate solution is 1: 2.5;
(4) spraying: and (3) carrying out electrostatic spraying on the polyurethane prepolymer solution to obtain the toughening agent.
Wherein the catalyst is triethanolamine.
Wherein the particle size of the nano silicon dioxide is 120nm, and the particle size of the toughening agent is 30.4 mu m.
Wherein the plasticizer is trioctyl trimellitate.
Wherein the heat stabilizer is a calcium-zinc composite heat stabilizer.
The flame retardant consists of ammonium polyphosphate, triphenyl phosphate and aluminum hydroxide according to the weight ratio of 1:2: 0.5.
Wherein the antioxidant consists of an antioxidant 168 and an antioxidant 1010 according to the weight ratio of 1: 1.
Wherein the lubricant is calcium stearate.
The flame-retardant and aging-resistant plastic shell is prepared by the following method: weighing the raw materials in parts by weight, dispersing and mixing, then carrying out melt extrusion granulation, and carrying out injection molding to obtain the flame-retardant and aging-resistant plastic shell.
Example 5
The flame-retardant and aging-resistant plastic shell comprises the following raw materials in parts by weight:
the preparation method of the toughening agent comprises the following steps:
(1) alcoholysis: carrying out alcoholysis reaction on castor oil and glycerol under the catalysis of a catalyst, wherein the reaction temperature is 215 ℃, the reaction time is 2.2 hours, and alcoholysis castor oil is obtained, and the castor oil, the glycerol and the catalyst are prepared according to the weight ratio of 500:110: 2;
(2) modification: dissolving 2, 4-toluene diisocyanate in N, N-dimethylacetamide, adding nano silicon dioxide, stirring and mixing to obtain an isocyanate solution, wherein the weight ratio of the 2, 4-toluene diisocyanate to the nano silicon dioxide to the N, N-dimethylacetamide is 6:2: 10;
(3) and (3) polyurethane synthesis: adding the alcoholysis castor oil into an isocyanate solution for reaction at 65 ℃ for 2.8 hours to obtain a polyurethane prepolymer solution, wherein the weight ratio of the alcoholysis castor oil to the isocyanate solution is 1: 3;
(4) spraying: and (3) carrying out electrostatic spraying on the polyurethane prepolymer solution to obtain the toughening agent.
Wherein the catalyst is triethanolamine.
Wherein the particle size of the nano silicon dioxide is 170nm, and the particle size of the toughening agent is 16.7 mu m.
Wherein the plasticizer is dioctyl adipate.
Wherein the heat stabilizer is a calcium-zinc composite heat stabilizer.
The flame retardant consists of ammonium polyphosphate, triphenyl phosphate and aluminum hydroxide according to the weight ratio of 2:1: 0.6.
Wherein the antioxidant consists of an antioxidant 168 and an antioxidant 1010 according to the weight ratio of 1: 1.
Wherein the lubricant is polyethylene wax.
The flame-retardant and aging-resistant plastic shell is prepared by the following method: weighing the raw materials in parts by weight, dispersing and mixing, then carrying out melt extrusion granulation, and carrying out injection molding to obtain the flame-retardant and aging-resistant plastic shell.
Comparative example 1
This comparative example differs from example 1 in that: the toughening agent consists of ACR and CPE according to the weight ratio of 1: 1.
Comparative example 2
This comparative example differs from example 1 in that: the toughening agent is prepared by the following method:
(1) alcoholysis: carrying out alcoholysis reaction on castor oil and glycerol under the catalysis of a catalyst, wherein the reaction temperature is 200 ℃, the reaction time is 1.5 hours, and alcoholysis castor oil is obtained, and the castor oil, the glycerol and the catalyst are prepared according to the weight ratio of 500:80: 1;
(2) modification: dissolving 2, 4-toluene diisocyanate in N, N-dimethylacetamide to obtain an isocyanate solution, wherein the weight ratio of the 2, 4-toluene diisocyanate to the N, N-dimethylacetamide is 5: 10;
(3) and (3) polyurethane synthesis: adding the alcoholysis castor oil into an isocyanate solution for reaction at 50 ℃ for 2 hours to obtain a polyurethane prepolymer solution, wherein the weight ratio of the alcoholysis castor oil to the isocyanate solution is 1: 2;
(4) spraying: and (3) carrying out electrostatic spraying on the polyurethane prepolymer solution to obtain the toughening agent.
Tensile strength, flexural strength, impact strength and flame retardancy were measured for examples 1-5 and comparative examples 1-2, and the following table was obtained:
the data in the table show that the flame-retardant and aging-resistant plastic shell has excellent mechanical properties, and the flame-retardant properties can reach V0 level, thereby meeting the requirement of high flame retardance; it can be seen from the comparison between example 1 and comparative example 1 that the toughening agent of the present invention is superior to conventional ACR and CPE in toughening effect and can significantly improve the flexural strength and tensile strength of the plastic shell; it can be seen from the comparison between comparative example 1 and comparative example 2 that the polyurethane toughening agent has a significant improvement in bending strength and tensile strength, but lacks the toughening effect of the nano silica rigid particles in improving the impact resistance.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (10)
1. A flame-retardant and aging-resistant plastic shell is characterized in that: the feed comprises the following raw materials in parts by weight:
the preparation method of the toughening agent comprises the following steps:
(1) alcoholysis: carrying out alcoholysis reaction on castor oil and glycerol under the catalysis of a catalyst, wherein the reaction temperature is 200-220 ℃, and the reaction time is 1.5-2.5h, so as to obtain alcoholysis castor oil, and the weight ratio of the castor oil to the glycerol to the catalyst is 500:80-120: 1-3;
(2) modification: dissolving 2, 4-toluene diisocyanate in N, N-dimethylacetamide, adding nano silicon dioxide, stirring and mixing to obtain an isocyanate solution, wherein the weight ratio of the 2, 4-toluene diisocyanate to the nano silicon dioxide to the N, N-dimethylacetamide is 5-7:1-2: 10;
(3) and (3) polyurethane synthesis: adding the alcoholysis castor oil into an isocyanate solution for reaction at the temperature of 50-70 ℃ for 2-3h to obtain a polyurethane prepolymer solution, wherein the weight ratio of the alcoholysis castor oil to the isocyanate solution is 1: 2-4;
(4) spraying: and (3) carrying out electrostatic spraying on the polyurethane prepolymer solution to obtain the toughening agent.
2. The flame-retardant aging-resistant plastic shell according to claim 1, wherein: the catalyst is triethanolamine.
3. The flame-retardant aging-resistant plastic shell according to claim 1, wherein: the particle size of the nano silicon dioxide is 100-200nm, and the particle size of the toughening agent is 26.3-41.5 mu m.
4. The flame-retardant aging-resistant plastic shell according to claim 1, wherein: the plasticizer is at least one of trioctyl trimellitate, dioctyl adipate and dioctyl sebacate.
5. The flame-retardant aging-resistant plastic shell according to claim 1, wherein: the plasticizer consists of trioctyl trimellitate, dioctyl adipate and dioctyl sebacate in a weight ratio of 1-2:1-2: 1.
6. The flame-retardant aging-resistant plastic shell according to claim 1, wherein: the heat stabilizer is a calcium-zinc composite heat stabilizer.
7. The flame-retardant aging-resistant plastic shell according to claim 1, wherein: the flame retardant consists of ammonium polyphosphate, triphenyl phosphate and aluminum hydroxide according to the weight ratio of 1-3:1-2: 0.4-0.6.
8. The flame-retardant aging-resistant plastic shell according to claim 1, wherein: the antioxidant consists of an antioxidant 168 and an antioxidant 1010 according to the weight ratio of 1: 1.
9. The flame-retardant aging-resistant plastic shell according to claim 1, wherein: the lubricant is at least one of talcum powder, calcium stearate and polyethylene wax.
10. The flame-retardant aging-resistant plastic shell according to claim 1, wherein: the preparation method comprises the following steps: weighing the raw materials in parts by weight, dispersing and mixing, then carrying out melt extrusion granulation, and carrying out injection molding to obtain the flame-retardant and aging-resistant plastic shell.
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| CN110591158B (en) * | 2019-09-24 | 2021-10-08 | 浙江华峰新材料有限公司 | Modified core-shell type aluminum oxide and polyurethane composite material, and preparation method and application thereof |
| CN111073174B (en) * | 2019-12-25 | 2021-12-31 | 广东祺龙科技有限公司 | Odorless antistatic PVC composite material and preparation method thereof |
| CN113105696A (en) * | 2021-05-25 | 2021-07-13 | 荔浦纬通新材料有限公司 | Preparation method of polypropylene composite engineering plastic |
| CN113337038A (en) * | 2021-06-01 | 2021-09-03 | 北京凌增新材料科技有限责任公司 | Preparation method of plastic with flame retardant property |
| CN114736471A (en) * | 2022-04-11 | 2022-07-12 | 界首市锦丰塑业有限公司 | Production process of toughened waste polyvinyl chloride |
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