CN109851946B - Flame-retardant and aging-resistant plastic shell - Google Patents
Flame-retardant and aging-resistant plastic shell Download PDFInfo
- Publication number
- CN109851946B CN109851946B CN201811636916.0A CN201811636916A CN109851946B CN 109851946 B CN109851946 B CN 109851946B CN 201811636916 A CN201811636916 A CN 201811636916A CN 109851946 B CN109851946 B CN 109851946B
- Authority
- CN
- China
- Prior art keywords
- flame
- retardant
- aging
- plastic shell
- resistant plastic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 48
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229920003023 plastic Polymers 0.000 title claims abstract description 41
- 239000004033 plastic Substances 0.000 title claims abstract description 41
- 230000032683 aging Effects 0.000 title claims abstract description 39
- 235000019438 castor oil Nutrition 0.000 claims abstract description 49
- 239000004359 castor oil Substances 0.000 claims abstract description 49
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims abstract description 49
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000012745 toughening agent Substances 0.000 claims abstract description 37
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 21
- 229920002635 polyurethane Polymers 0.000 claims abstract description 17
- 239000004814 polyurethane Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000004014 plasticizer Substances 0.000 claims abstract description 13
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 239000000314 lubricant Substances 0.000 claims abstract description 9
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 41
- 238000006136 alcoholysis reaction Methods 0.000 claims description 28
- 239000012948 isocyanate Substances 0.000 claims description 24
- 150000002513 isocyanates Chemical class 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 18
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 16
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 16
- 230000035484 reaction time Effects 0.000 claims description 15
- 238000005507 spraying Methods 0.000 claims description 15
- 238000001746 injection moulding Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000005543 nano-size silicon particle Substances 0.000 claims description 9
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 8
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 7
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 7
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 7
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical group [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 7
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 7
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 7
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 7
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 7
- 238000005469 granulation Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 5
- -1 polyethylene Polymers 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 4
- 235000013539 calcium stearate Nutrition 0.000 claims description 4
- 239000008116 calcium stearate Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims 1
- 238000007590 electrostatic spraying Methods 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 229920001971 elastomer Polymers 0.000 abstract description 3
- 239000000806 elastomer Substances 0.000 abstract description 3
- 230000007246 mechanism Effects 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 20
- 229920000915 polyvinyl chloride Polymers 0.000 description 19
- 235000011187 glycerol Nutrition 0.000 description 14
- 238000000034 method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- LADVLFVCTCHOAI-UHFFFAOYSA-N isocyanic acid;toluene Chemical compound N=C=O.CC1=CC=CC=C1 LADVLFVCTCHOAI-UHFFFAOYSA-N 0.000 description 6
- 239000004609 Impact Modifier Substances 0.000 description 4
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明涉及塑料壳技术领域，具体涉及一种阻燃耐老化塑料壳，原料包括PVC、增塑剂、热稳定剂、阻燃剂、增韧剂、抗氧化剂和润滑剂，增韧剂主要通过蓖麻油、2，4‑二异氰酸甲苯酯和纳米二氧化硅制得。本发明在PVC中加入阻燃剂、热稳定剂和抗氧化剂，使PVC复合材料具有较好的阻燃性和耐老化性，而为了提高PVC的抗冲击性，本发明采用蓖麻油聚氨酯对纳米二氧化硅进行包覆制得增韧剂，包覆处理改善纳米二氧化硅在PVC中的分散性，因此增韧效果较好，同时蓖麻油聚氨酯也具有较好的弹性，因此本发明的增韧剂通过弹性体增韧和刚性增韧的两种截然不同的机理协同增强PVC的韧性，使PVC具有优良的抗冲击性能，符合插头外壳的性能需求。The invention relates to the technical field of plastic shells, in particular to a flame-retardant and aging-resistant plastic shell. The raw materials include PVC, a plasticizer, a heat stabilizer, a flame retardant, a toughening agent, an antioxidant and a lubricant. It is prepared from castor oil, 2,4-diisocyanate tolyl and nano-silica. In the present invention, flame retardants, heat stabilizers and antioxidants are added to the PVC, so that the PVC composite material has better flame retardancy and aging resistance, and in order to improve the impact resistance of PVC, the present invention adopts castor oil polyurethane to Silica is coated to obtain a toughening agent, and the coating treatment improves the dispersion of nano-silica in PVC, so the toughening effect is good, and at the same time, castor oil polyurethane also has good elasticity. The toughening agent synergistically enhances the toughness of PVC through two distinct mechanisms of elastomer toughening and rigid toughening, so that PVC has excellent impact resistance and meets the performance requirements of the plug shell.
Description
技术领域technical field
本发明涉及塑料壳技术领域，具体涉及一种阻燃耐老化塑料壳。The invention relates to the technical field of plastic shells, in particular to a flame-retardant and aging-resistant plastic shell.
背景技术Background technique
插头是电源线连接强电的关键部件，所以其性能的优劣直接影响安全使用，其中电源线插头在大功率场合工作过程中容易发热，或者在承载瞬间高压时产生打火现象，这些热量或火花都可能成为火灾的起源引起燃烧，必须引起重视。The plug is a key component for the power cord to connect to strong electricity, so its performance directly affects the safe use. The power cord plug is prone to heat during the working process of high-power occasions, or sparks when it carries instantaneous high voltage. These heat or Sparks can be the source of fire and cause burning, and attention must be paid.
聚氯乙烯(PVC)因其物理机械性能好、电绝缘性优越、注塑工艺简单、而且价格便宜，广泛用于注塑成型各种电源线插头，用于插头料的PVC材料主要由PVC树脂、增塑剂、热稳定剂、阻燃剂、抗冲击改性剂等组成。Polyvinyl chloride (PVC) is widely used in injection molding of various power cord plugs because of its good physical and mechanical properties, superior electrical insulation, simple injection molding process and low price. Plasticizer, heat stabilizer, flame retardant, impact modifier, etc.
但PVC的抗冲击性能较差，阻燃性和耐老化性也有所欠缺。However, the impact resistance of PVC is poor, and its flame retardancy and aging resistance are also lacking.
发明内容SUMMARY OF THE INVENTION
为了克服现有技术中存在的缺点和不足，本发明的目的在于提供一种阻燃耐老化塑料壳。In order to overcome the shortcomings and deficiencies in the prior art, the purpose of the present invention is to provide a flame-retardant and aging-resistant plastic shell.
本发明的目的通过下述技术方案实现：The object of the present invention is achieved through the following technical solutions:
一种阻燃耐老化塑料壳，包括如下重量份的原料：A flame-retardant and aging-resistant plastic shell, comprising the following raw materials by weight:
其中，所述增韧剂的制备方法包括如下步骤：Wherein, the preparation method of described toughening agent comprises the steps:
(1)醇解：取蓖麻油和甘油在催化剂的催化下进行醇解反应，反应温度为200-220℃，反应时间为1.5-2.5h，得到醇解蓖麻油，所述蓖麻油、甘油和催化剂的重量比为500:80-120:1-3的比例组成；(1) Alcoholysis: get castor oil and glycerin to carry out alcoholysis reaction under the catalysis of catalyst, reaction temperature is 200-220 ℃, and reaction time is 1.5-2.5h, obtains alcoholysis castor oil, described castor oil, glycerol and The weight ratio of the catalyst is 500:80-120:1-3;
(2)改性：取2，4-二异氰酸甲苯酯溶于N，N-二甲基乙酰胺中，加入纳米二氧化硅进行搅拌混合，得到异氰酸酯溶液，所述2，4-二异氰酸甲苯酯、纳米二氧化硅和N，N-二甲基乙酰胺的重量比为5-7:1-2:10；(2) Modification: Dissolve 2,4-diisocyanate tolyl in N,N-dimethylacetamide, add nano-silica to stir and mix to obtain an isocyanate solution, the 2,4-diisocyanate The weight ratio of toluene isocyanate, nano-silica and N,N-dimethylacetamide is 5-7:1-2:10;
(3)聚氨酯合成：将所述醇解蓖麻油加入至异氰酸酯溶液中进行反应，反应温度为50-70℃，反应时间为2-3h，即得到聚氨酯预聚体溶液，醇解蓖麻油与异氰酸酯溶液的重量比为1:2-4；(3) Polyurethane synthesis: add the alcoholyzed castor oil to the isocyanate solution for reaction, the reaction temperature is 50-70°C, and the reaction time is 2-3h, to obtain a polyurethane prepolymer solution, alcoholysis castor oil and isocyanate The weight ratio of the solution is 1:2-4;
(4)喷雾：将所述聚氨酯预聚体溶液进行静电喷雾，即得到所述增韧剂。(4) Spraying: electrostatically spraying the polyurethane prepolymer solution to obtain the toughening agent.
本发明在PVC中加入阻燃剂、热稳定剂和抗氧化剂，使PVC复合材料符合插头需要的阻燃性和耐老化性，而为了提高PVC的抗冲击性，本发明加入了特制增韧剂。现有技术中，适用于PVC的抗冲击改性剂一般为CPE、ACR、MBS等，这几种抗冲击改性剂各有优劣，但目前这几款抗冲击改性剂主要依赖于进口，成本较高，而成本较低的刚性增韧粒子需要起到较好的增韧作用的话，对分散性的要求很高。本发明采用蓖麻油聚氨酯对纳米二氧化硅进行包覆制得增韧剂，包覆处理改善纳米二氧化硅在PVC中的分散性，因此增韧效果较好，同时蓖麻油聚氨酯也具有较好的弹性，因此本发明的增韧剂通过弹性体增韧和刚性增韧的两种截然不同的机理协同增强PVC的韧性，使PVC具有优良的抗冲击性能，符合插头外壳的性能需求。In the present invention, flame retardants, heat stabilizers and antioxidants are added to the PVC, so that the PVC composite material meets the flame retardancy and aging resistance required by the plug, and in order to improve the impact resistance of the PVC, the present invention adds a special toughening agent . In the prior art, the impact modifiers suitable for PVC are generally CPE, ACR, MBS, etc. These impact modifiers have their own advantages and disadvantages, but at present these impact modifiers mainly rely on imported products. , the cost is higher, and if the rigid toughened particles with lower cost need to play a better toughening role, the requirements for dispersibility are very high. The present invention adopts castor oil polyurethane to coat nano-silicon dioxide to obtain a toughening agent, and the coating treatment improves the dispersibility of nano-silicon dioxide in PVC, so the toughening effect is good, and at the same time, the castor oil polyurethane also has a good toughening effect. Therefore, the toughening agent of the present invention synergistically enhances the toughness of PVC through two distinct mechanisms of elastomer toughening and rigid toughening, so that PVC has excellent impact resistance and meets the performance requirements of the plug shell.
其中，所述催化剂为三乙醇胺。三乙醇胺作为反应型催化剂可以提升蓖麻油的醇解效率，改变蓖麻油的分子结构，提高制得的聚氨酯韧性。Wherein, the catalyst is triethanolamine. As a reactive catalyst, triethanolamine can improve the alcoholysis efficiency of castor oil, change the molecular structure of castor oil, and improve the toughness of the prepared polyurethane.
其中，所述纳米二氧化硅的粒径为100-200nm，所述增韧剂的粒径为26.3-41.5μm。本发明采用聚氨酯对纳米二氧化硅进行包覆，因而可以采用纳米直径的二氧化硅，解决纳米二氧化硅的易团聚问题，同时为了避免喷雾过程中二氧化硅的自身团聚，因此粒径优选为100-200nm，并且通过控制纳米二氧化硅的粒径后，增韧剂的粒径也得到了控制，制得的微米级增韧剂在PVC中可以具有较好的分散性，起到显著的增韧作用。Wherein, the particle size of the nano-silica is 100-200 nm, and the particle size of the toughening agent is 26.3-41.5 μm. In the present invention, the nano-silicon dioxide is coated with polyurethane, so the nano-diameter silicon dioxide can be used to solve the problem of easy agglomeration of the nano-silicon dioxide. It is 100-200nm, and by controlling the particle size of nano-silica, the particle size of the toughening agent is also controlled, and the obtained micron-level toughening agent can have good dispersibility in PVC, which plays a significant role in toughening effect.
其中，所述增塑剂为偏苯三酸三辛酯、己二酸二辛酯和癸二酸二辛酯中的至少一种。增塑剂的作用在于提高PVC的加工流动性，利于各物料的混合分散。Wherein, the plasticizer is at least one of trioctyl trimellitate, dioctyl adipate and dioctyl sebacate. The function of plasticizer is to improve the processing fluidity of PVC, which is conducive to the mixing and dispersion of various materials.
其中，所述增塑剂由偏苯三酸三辛酯、己二酸二辛酯和癸二酸二辛酯按重量比1-2:1-2:1的比例组成。本发明复配选用的增塑剂对于PVC的加工性提升是显著的，利于增韧剂、热稳定剂等各助剂在PVC中的均匀分布，因为塑料壳不容易发生局部老化，稳定性更高。Wherein, the plasticizer is composed of trioctyl trimellitate, dioctyl adipate and dioctyl sebacate in a weight ratio of 1-2:1-2:1. The plasticizer selected for compounding in the present invention significantly improves the processability of PVC, and is conducive to the uniform distribution of various additives such as toughening agent and heat stabilizer in PVC, because the plastic shell is not prone to local aging and has better stability. high.
其中，所述热稳定剂为钙锌复合热稳定剂。Wherein, the heat stabilizer is a calcium-zinc composite heat stabilizer.
其中，所述阻燃剂由聚磷酸铵、磷酸三苯酯和氢氧化铝按重量比1-3:1-2:0.4-0.6的比例组成。本发明复配选用的阻燃剂在尽量不影响塑料壳的力学性能时，可以使塑料壳的阻燃性达到V0级别，并且提高塑料壳的热稳定性。Wherein, the flame retardant is composed of ammonium polyphosphate, triphenyl phosphate and aluminum hydroxide in a weight ratio of 1-3:1-2:0.4-0.6. The flame retardant selected for compounding in the present invention can make the flame retardancy of the plastic shell reach V0 level and improve the thermal stability of the plastic shell when the mechanical properties of the plastic shell are not affected as much as possible.
其中，所述抗氧化剂由抗氧剂168和抗氧剂1010按重量比1:1的比例组成。Wherein, the antioxidant is composed of antioxidant 168 and antioxidant 1010 in a weight ratio of 1:1.
其中，所述润滑剂为滑石粉、硬脂酸钙和聚乙烯蜡中的至少一种。润滑剂可以提高熔融流动性和脱模性，利于增韧剂、热稳定剂等各助剂在PVC中的均匀分布，降低加工难度。Wherein, the lubricant is at least one of talc, calcium stearate and polyethylene wax. Lubricants can improve melt fluidity and mold release properties, facilitate the uniform distribution of various additives such as tougheners and heat stabilizers in PVC, and reduce processing difficulties.
所述阻燃耐老化塑料壳，通过如下方法制得：按重量份数称取各原料进行分散混合，然后进行熔融挤出造粒，注塑成型，即得到所述的阻燃耐老化塑料壳。The flame-retardant and aging-resistant plastic shell is prepared by the following method: weighing each raw material by weight, dispersing and mixing, then performing melt extrusion and granulation, and injection molding to obtain the flame-retardant and aging-resistant plastic shell.
本发明的有益效果在于：本发明在PVC中加入阻燃剂、热稳定剂和抗氧化剂，使PVC复合材料符合插头需要的阻燃性和耐老化性，而为了提高PVC的抗冲击性，本发明采用蓖麻油聚氨酯对纳米二氧化硅进行包覆制得增韧剂，包覆处理改善纳米二氧化硅在PVC中的分散性，因此增韧效果较好，同时蓖麻油聚氨酯也具有较好的弹性，因此本发明的增韧剂通过弹性体增韧和刚性增韧的两种截然不同的机理协同增强PVC的韧性，使PVC具有优良的抗冲击性能，符合插头外壳的性能需求。The beneficial effects of the present invention are: the present invention adds flame retardants, heat stabilizers and antioxidants to the PVC, so that the PVC composite material meets the flame retardancy and aging resistance required by the plug, and in order to improve the impact resistance of the PVC, the present invention has the following advantages: The invention adopts castor oil polyurethane to coat nano-silicon dioxide to obtain a toughening agent, and the coating treatment improves the dispersibility of nano-silicon dioxide in PVC, so the toughening effect is good, and the castor oil polyurethane also has good toughness. Therefore, the toughening agent of the present invention synergistically enhances the toughness of PVC through two distinct mechanisms of elastomer toughening and rigid toughening, so that PVC has excellent impact resistance and meets the performance requirements of the plug shell.
具体实施方式Detailed ways
为了便于本领域技术人员的理解，下面结合实施例对本发明作进一步的说明，实施方式提及的内容并非对本发明的限定。In order to facilitate the understanding of those skilled in the art, the present invention will be further described below with reference to the examples, and the contents mentioned in the embodiments are not intended to limit the present invention.
实施例1Example 1
一种阻燃耐老化塑料壳，包括如下重量份的原料：A flame-retardant and aging-resistant plastic shell, comprising the following raw materials by weight:
其中，所述增韧剂的制备方法包括如下步骤：Wherein, the preparation method of described toughening agent comprises the steps:
(1)醇解：取蓖麻油和甘油在催化剂的催化下进行醇解反应，反应温度为210℃，反应时间为2h，得到醇解蓖麻油，所述蓖麻油、甘油和催化剂的重量比为500:100:2的比例组成；(1) alcoholysis: get castor oil and glycerol and carry out alcoholysis reaction under the catalysis of catalyzer, reaction temperature is 210 ℃, and the reaction time is 2h, obtains alcoholysis castor oil, and the weight ratio of described castor oil, glycerol and catalyzer is 500:100:2 ratio composition;
(2)改性：取2，4-二异氰酸甲苯酯溶于N，N-二甲基乙酰胺中，加入纳米二氧化硅进行搅拌混合，得到异氰酸酯溶液，所述2，4-二异氰酸甲苯酯、纳米二氧化硅和N，N-二甲基乙酰胺的重量比为6:1.5:10；(2) Modification: Dissolve 2,4-diisocyanate tolyl in N,N-dimethylacetamide, add nano-silica to stir and mix to obtain an isocyanate solution, the 2,4-diisocyanate The weight ratio of toluene isocyanate, nano-silica and N,N-dimethylacetamide is 6:1.5:10;
(3)聚氨酯合成：将所述醇解蓖麻油加入至异氰酸酯溶液中进行反应，反应温度为60℃，反应时间为2.5h，即得到聚氨酯预聚体溶液，醇解蓖麻油与异氰酸酯溶液的重量比为1:3；(3) Polyurethane synthesis: add the alcoholyzed castor oil to the isocyanate solution for reaction, the reaction temperature is 60°C, and the reaction time is 2.5h, to obtain a polyurethane prepolymer solution, the weight of the alcoholyzed castor oil and the isocyanate solution The ratio is 1:3;
(4)喷雾：将所述聚氨酯预聚体溶液进行静电喷雾，即得到所述增韧剂。(4) Spraying: electrostatically spraying the polyurethane prepolymer solution to obtain the toughening agent.
其中，所述催化剂为三乙醇胺。Wherein, the catalyst is triethanolamine.
其中，所述纳米二氧化硅的粒径为150nm，所述增韧剂的粒径为34.1μm。Wherein, the particle size of the nano-silica is 150 nm, and the particle size of the toughening agent is 34.1 μm.
其中，所述增塑剂由偏苯三酸三辛酯、己二酸二辛酯和癸二酸二辛酯按重量比1.5:1.5:1的比例组成。Wherein, the plasticizer is composed of trioctyl trimellitate, dioctyl adipate and dioctyl sebacate in a weight ratio of 1.5:1.5:1.
其中，所述热稳定剂为钙锌复合热稳定剂。Wherein, the heat stabilizer is a calcium-zinc composite heat stabilizer.
其中，所述阻燃剂由聚磷酸铵、磷酸三苯酯和氢氧化铝按重量比2:1.5:0.5的比例组成。Wherein, the flame retardant is composed of ammonium polyphosphate, triphenyl phosphate and aluminum hydroxide in a weight ratio of 2:1.5:0.5.
其中，所述抗氧化剂由抗氧剂168和抗氧剂1010按重量比1:1的比例组成。Wherein, the antioxidant is composed of antioxidant 168 and antioxidant 1010 in a weight ratio of 1:1.
其中，所述润滑剂由滑石粉、硬脂酸钙和聚乙烯蜡按重量比1:1:2的比例组成。Wherein, the lubricant is composed of talc, calcium stearate and polyethylene wax in a weight ratio of 1:1:2.
所述阻燃耐老化塑料壳，通过如下方法制得：按重量份数称取各原料进行分散混合，然后进行熔融挤出造粒，注塑成型，即得到所述的阻燃耐老化塑料壳。The flame-retardant and aging-resistant plastic shell is prepared by the following method: weighing each raw material by weight, dispersing and mixing, then performing melt extrusion and granulation, and injection molding to obtain the flame-retardant and aging-resistant plastic shell.
实施例2Example 2
一种阻燃耐老化塑料壳，包括如下重量份的原料：A flame-retardant and aging-resistant plastic shell, comprising the following raw materials by weight:
其中，所述增韧剂的制备方法包括如下步骤：Wherein, the preparation method of described toughening agent comprises the steps:
(1)醇解：取蓖麻油和甘油在催化剂的催化下进行醇解反应，反应温度为200℃，反应时间为1.5h，得到醇解蓖麻油，所述蓖麻油、甘油和催化剂的重量比为500:80:1的比例组成；(1) alcoholysis: get castor oil and glycerol and carry out alcoholysis reaction under the catalysis of catalyst, reaction temperature is 200 ℃, and reaction time is 1.5h, obtains alcoholysis castor oil, the weight ratio of described castor oil, glycerol and catalyst It is composed of a ratio of 500:80:1;
(2)改性：取2，4-二异氰酸甲苯酯溶于N，N-二甲基乙酰胺中，加入纳米二氧化硅进行搅拌混合，得到异氰酸酯溶液，所述2，4-二异氰酸甲苯酯、纳米二氧化硅和N，N-二甲基乙酰胺的重量比为5:1:10；(2) Modification: Dissolve 2,4-diisocyanate tolyl in N,N-dimethylacetamide, add nano-silica to stir and mix to obtain an isocyanate solution, the 2,4-diisocyanate The weight ratio of toluene isocyanate, nano-silica and N,N-dimethylacetamide is 5:1:10;
(3)聚氨酯合成：将所述醇解蓖麻油加入至异氰酸酯溶液中进行反应，反应温度为50℃，反应时间为2h，即得到聚氨酯预聚体溶液，醇解蓖麻油与异氰酸酯溶液的重量比为1:2；(3) Polyurethane synthesis: add the alcoholyzed castor oil to the isocyanate solution for reaction, the reaction temperature is 50°C, and the reaction time is 2h, to obtain a polyurethane prepolymer solution, and the weight ratio of the alcoholyzed castor oil to the isocyanate solution is is 1:2;
(4)喷雾：将所述聚氨酯预聚体溶液进行静电喷雾，即得到所述增韧剂。(4) Spraying: electrostatically spraying the polyurethane prepolymer solution to obtain the toughening agent.
其中，所述催化剂为三乙醇胺。Wherein, the catalyst is triethanolamine.
其中，所述纳米二氧化硅的粒径为100nm，所述增韧剂的粒径为26.3μm。Wherein, the particle size of the nano silica is 100 nm, and the particle size of the toughening agent is 26.3 μm.
其中，所述增塑剂由偏苯三酸三辛酯、己二酸二辛酯和癸二酸二辛酯按重量比1:1:1的比例组成。Wherein, the plasticizer is composed of trioctyl trimellitate, dioctyl adipate and dioctyl sebacate in a weight ratio of 1:1:1.
其中，所述热稳定剂为钙锌复合热稳定剂。Wherein, the heat stabilizer is a calcium-zinc composite heat stabilizer.
其中，所述阻燃剂由聚磷酸铵、磷酸三苯酯和氢氧化铝按重量比1:1:0.4的比例组成。Wherein, the flame retardant is composed of ammonium polyphosphate, triphenyl phosphate and aluminum hydroxide in a weight ratio of 1:1:0.4.
其中，所述抗氧化剂由抗氧剂168和抗氧剂1010按重量比1:1的比例组成。Wherein, the antioxidant is composed of antioxidant 168 and antioxidant 1010 in a weight ratio of 1:1.
其中，所述润滑剂为滑石粉。Wherein, the lubricant is talc.
所述阻燃耐老化塑料壳，通过如下方法制得：按重量份数称取各原料进行分散混合，然后进行熔融挤出造粒，注塑成型，即得到所述的阻燃耐老化塑料壳。The flame-retardant and aging-resistant plastic shell is prepared by the following method: weighing each raw material by weight, dispersing and mixing, then performing melt extrusion and granulation, and injection molding to obtain the flame-retardant and aging-resistant plastic shell.
实施例3Example 3
一种阻燃耐老化塑料壳，包括如下重量份的原料：A flame-retardant and aging-resistant plastic shell, comprising the following raw materials by weight:
其中，所述增韧剂的制备方法包括如下步骤：Wherein, the preparation method of described toughening agent comprises the steps:
(1)醇解：取蓖麻油和甘油在催化剂的催化下进行醇解反应，反应温度为220℃，反应时间为2.5h，得到醇解蓖麻油，所述蓖麻油、甘油和催化剂的重量比为500:120:3的比例组成；(1) alcoholysis: get castor oil and glycerol and carry out alcoholysis reaction under the catalysis of catalyst, reaction temperature is 220 ℃, and reaction time is 2.5h, obtains alcoholysis castor oil, the weight ratio of described castor oil, glycerol and catalyst It is composed of a ratio of 500:120:3;
(2)改性：取2，4-二异氰酸甲苯酯溶于N，N-二甲基乙酰胺中，加入纳米二氧化硅进行搅拌混合，得到异氰酸酯溶液，所述2，4-二异氰酸甲苯酯、纳米二氧化硅和N，N-二甲基乙酰胺的重量比为7:2:10；(2) Modification: Dissolve 2,4-diisocyanate tolyl in N,N-dimethylacetamide, add nano-silica to stir and mix to obtain an isocyanate solution, the 2,4-diisocyanate The weight ratio of toluene isocyanate, nano-silica and N,N-dimethylacetamide is 7:2:10;
(3)聚氨酯合成：将所述醇解蓖麻油加入至异氰酸酯溶液中进行反应，反应温度为70℃，反应时间为3h，即得到聚氨酯预聚体溶液，醇解蓖麻油与异氰酸酯溶液的重量比为1:4；(3) Polyurethane synthesis: add the alcoholyzed castor oil to the isocyanate solution for reaction, the reaction temperature is 70°C, and the reaction time is 3h, to obtain a polyurethane prepolymer solution, and the weight ratio of the alcoholyzed castor oil to the isocyanate solution is is 1:4;
(4)喷雾：将所述聚氨酯预聚体溶液进行静电喷雾，即得到所述增韧剂。(4) Spraying: electrostatically spraying the polyurethane prepolymer solution to obtain the toughening agent.
其中，所述催化剂为三乙醇胺。Wherein, the catalyst is triethanolamine.
其中，所述纳米二氧化硅的粒径为200nm，所述增韧剂的粒径为41.5μm。Wherein, the particle size of the nano-silica is 200 nm, and the particle size of the toughening agent is 41.5 μm.
其中，所述增塑剂由偏苯三酸三辛酯、己二酸二辛酯和癸二酸二辛酯按重量比2:2:1的比例组成。Wherein, the plasticizer is composed of trioctyl trimellitate, dioctyl adipate and dioctyl sebacate in a weight ratio of 2:2:1.
其中，所述热稳定剂为钙锌复合热稳定剂。Wherein, the heat stabilizer is a calcium-zinc composite heat stabilizer.
其中，所述阻燃剂由聚磷酸铵、磷酸三苯酯和氢氧化铝按重量比3:2:0.6的比例组成。Wherein, the flame retardant is composed of ammonium polyphosphate, triphenyl phosphate and aluminum hydroxide in a weight ratio of 3:2:0.6.
其中，所述抗氧化剂由抗氧剂168和抗氧剂1010按重量比1:1的比例组成。Wherein, the antioxidant is composed of antioxidant 168 and antioxidant 1010 in a weight ratio of 1:1.
其中，所述润滑剂为聚乙烯蜡。Wherein, the lubricant is polyethylene wax.
所述阻燃耐老化塑料壳，通过如下方法制得：按重量份数称取各原料进行分散混合，然后进行熔融挤出造粒，注塑成型，即得到所述的阻燃耐老化塑料壳。The flame-retardant and aging-resistant plastic shell is prepared by the following method: weighing each raw material by weight, dispersing and mixing, then performing melt extrusion and granulation, and injection molding to obtain the flame-retardant and aging-resistant plastic shell.
实施例4Example 4
一种阻燃耐老化塑料壳，包括如下重量份的原料：A flame-retardant and aging-resistant plastic shell, comprising the following raw materials by weight:
其中，所述增韧剂的制备方法包括如下步骤：Wherein, the preparation method of described toughening agent comprises the steps:
(1)醇解：取蓖麻油和甘油在催化剂的催化下进行醇解反应，反应温度为205℃，反应时间为1.8h，得到醇解蓖麻油，所述蓖麻油、甘油和催化剂的重量比为500:90:1.5的比例组成；(1) alcoholysis: get castor oil and glycerol and carry out alcoholysis reaction under the catalysis of catalyst, reaction temperature is 205 ℃, and the reaction time is 1.8h, obtains alcoholysis castor oil, the weight ratio of described castor oil, glycerol and catalyst It is composed of a ratio of 500:90:1.5;
(2)改性：取2，4-二异氰酸甲苯酯溶于N，N-二甲基乙酰胺中，加入纳米二氧化硅进行搅拌混合，得到异氰酸酯溶液，所述2，4-二异氰酸甲苯酯、纳米二氧化硅和N，N-二甲基乙酰胺的重量比为6:1:10；(2) Modification: Dissolve 2,4-diisocyanate tolyl in N,N-dimethylacetamide, add nano-silica to stir and mix to obtain an isocyanate solution, the 2,4-diisocyanate The weight ratio of toluene isocyanate, nano-silica and N,N-dimethylacetamide is 6:1:10;
(3)聚氨酯合成：将所述醇解蓖麻油加入至异氰酸酯溶液中进行反应，反应温度为55℃，反应时间为2.2h，即得到聚氨酯预聚体溶液，醇解蓖麻油与异氰酸酯溶液的重量比为1:2.5；(3) Polyurethane synthesis: add the alcoholyzed castor oil to the isocyanate solution for reaction, the reaction temperature is 55°C, and the reaction time is 2.2h, to obtain the polyurethane prepolymer solution, the weight of the alcoholyzed castor oil and the isocyanate solution The ratio is 1:2.5;
(4)喷雾：将所述聚氨酯预聚体溶液进行静电喷雾，即得到所述增韧剂。(4) Spraying: electrostatically spraying the polyurethane prepolymer solution to obtain the toughening agent.
其中，所述催化剂为三乙醇胺。Wherein, the catalyst is triethanolamine.
其中，所述纳米二氧化硅的粒径为120nm，所述增韧剂的粒径为30.4μm。Wherein, the particle size of the nano-silica is 120 nm, and the particle size of the toughening agent is 30.4 μm.
其中，所述增塑剂为偏苯三酸三辛酯。Wherein, the plasticizer is trioctyl trimellitate.
其中，所述热稳定剂为钙锌复合热稳定剂。Wherein, the heat stabilizer is a calcium-zinc composite heat stabilizer.
其中，所述阻燃剂由聚磷酸铵、磷酸三苯酯和氢氧化铝按重量比1:2:0.5的比例组成。Wherein, the flame retardant is composed of ammonium polyphosphate, triphenyl phosphate and aluminum hydroxide in a weight ratio of 1:2:0.5.
其中，所述抗氧化剂由抗氧剂168和抗氧剂1010按重量比1:1的比例组成。Wherein, the antioxidant is composed of antioxidant 168 and antioxidant 1010 in a weight ratio of 1:1.
其中，所述润滑剂为硬脂酸钙。Wherein, the lubricant is calcium stearate.
所述阻燃耐老化塑料壳，通过如下方法制得：按重量份数称取各原料进行分散混合，然后进行熔融挤出造粒，注塑成型，即得到所述的阻燃耐老化塑料壳。The flame-retardant and aging-resistant plastic shell is prepared by the following method: weighing each raw material by weight, dispersing and mixing, then performing melt extrusion and granulation, and injection molding to obtain the flame-retardant and aging-resistant plastic shell.
实施例5Example 5
一种阻燃耐老化塑料壳，包括如下重量份的原料：A flame-retardant and aging-resistant plastic shell, comprising the following raw materials by weight:
其中，所述增韧剂的制备方法包括如下步骤：Wherein, the preparation method of described toughening agent comprises the steps:
(1)醇解：取蓖麻油和甘油在催化剂的催化下进行醇解反应，反应温度为215℃，反应时间为2.2h，得到醇解蓖麻油，所述蓖麻油、甘油和催化剂的重量比为500:110:2的比例组成；(1) alcoholysis: get castor oil and glycerol and carry out alcoholysis reaction under the catalysis of catalyst, reaction temperature is 215 ℃, and the reaction time is 2.2h, obtains alcoholysis castor oil, the weight ratio of described castor oil, glycerol and catalyst It is composed of a ratio of 500:110:2;
(2)改性：取2，4-二异氰酸甲苯酯溶于N，N-二甲基乙酰胺中，加入纳米二氧化硅进行搅拌混合，得到异氰酸酯溶液，所述2，4-二异氰酸甲苯酯、纳米二氧化硅和N，N-二甲基乙酰胺的重量比为6:2:10；(2) Modification: Dissolve 2,4-diisocyanate tolyl in N,N-dimethylacetamide, add nano-silica to stir and mix to obtain an isocyanate solution, the 2,4-diisocyanate The weight ratio of toluene isocyanate, nano-silica and N,N-dimethylacetamide is 6:2:10;
(3)聚氨酯合成：将所述醇解蓖麻油加入至异氰酸酯溶液中进行反应，反应温度为65℃，反应时间为2.8h，即得到聚氨酯预聚体溶液，醇解蓖麻油与异氰酸酯溶液的重量比为1:3；(3) Polyurethane synthesis: add the alcoholyzed castor oil to the isocyanate solution for reaction, the reaction temperature is 65°C, and the reaction time is 2.8h, to obtain the polyurethane prepolymer solution, the weight of the alcoholyzed castor oil and the isocyanate solution The ratio is 1:3;
(4)喷雾：将所述聚氨酯预聚体溶液进行静电喷雾，即得到所述增韧剂。(4) Spraying: electrostatically spraying the polyurethane prepolymer solution to obtain the toughening agent.
其中，所述催化剂为三乙醇胺。Wherein, the catalyst is triethanolamine.
其中，所述纳米二氧化硅的粒径为170nm，所述增韧剂的粒径为16.7μm。Wherein, the particle size of the nano-silica is 170 nm, and the particle size of the toughening agent is 16.7 μm.
其中，所述增塑剂为己二酸二辛酯。Wherein, the plasticizer is dioctyl adipate.
其中，所述热稳定剂为钙锌复合热稳定剂。Wherein, the heat stabilizer is a calcium-zinc composite heat stabilizer.
其中，所述阻燃剂由聚磷酸铵、磷酸三苯酯和氢氧化铝按重量比2:1:0.6的比例组成。Wherein, the flame retardant is composed of ammonium polyphosphate, triphenyl phosphate and aluminum hydroxide in a weight ratio of 2:1:0.6.
其中，所述抗氧化剂由抗氧剂168和抗氧剂1010按重量比1:1的比例组成。Wherein, the antioxidant is composed of antioxidant 168 and antioxidant 1010 in a weight ratio of 1:1.
其中，所述润滑剂为聚乙烯蜡。Wherein, the lubricant is polyethylene wax.
所述阻燃耐老化塑料壳，通过如下方法制得：按重量份数称取各原料进行分散混合，然后进行熔融挤出造粒，注塑成型，即得到所述的阻燃耐老化塑料壳。The flame-retardant and aging-resistant plastic shell is prepared by the following method: weighing each raw material by weight, dispersing and mixing, then performing melt extrusion and granulation, and injection molding to obtain the flame-retardant and aging-resistant plastic shell.
对比例1Comparative Example 1
本对比例与实施例1的区别在于：所述增韧剂由ACR和CPE按重量比1:1的比例组成。The difference between this comparative example and Example 1 is that the toughening agent is composed of ACR and CPE in a weight ratio of 1:1.
对比例2Comparative Example 2
本对比例与实施例1的区别在于：所述增韧剂通过如下方法制得：The difference between this comparative example and Example 1 is that the toughening agent is obtained by the following method:
(1)醇解：取蓖麻油和甘油在催化剂的催化下进行醇解反应，反应温度为200℃，反应时间为1.5h，得到醇解蓖麻油，所述蓖麻油、甘油和催化剂的重量比为500:80:1的比例组成；(1) alcoholysis: get castor oil and glycerol and carry out alcoholysis reaction under the catalysis of catalyst, reaction temperature is 200 ℃, and reaction time is 1.5h, obtains alcoholysis castor oil, the weight ratio of described castor oil, glycerol and catalyst It is composed of a ratio of 500:80:1;
(2)改性：取2，4-二异氰酸甲苯酯溶于N，N-二甲基乙酰胺中，得到异氰酸酯溶液，所述2，4-二异氰酸甲苯酯和N，N-二甲基乙酰胺的重量比为5:10；(2) Modification: Dissolve 2,4-diisocyanate tolyl in N,N-dimethylacetamide to obtain an isocyanate solution, the 2,4-diisocyanate tolyl and N,N - the weight ratio of dimethylacetamide is 5:10;
(3)聚氨酯合成：将所述醇解蓖麻油加入至异氰酸酯溶液中进行反应，反应温度为50℃，反应时间为2h，即得到聚氨酯预聚体溶液，醇解蓖麻油与异氰酸酯溶液的重量比为1:2；(3) Polyurethane synthesis: add the alcoholyzed castor oil to the isocyanate solution for reaction, the reaction temperature is 50°C, and the reaction time is 2h, to obtain a polyurethane prepolymer solution, and the weight ratio of the alcoholyzed castor oil to the isocyanate solution is is 1:2;
(4)喷雾：将所述聚氨酯预聚体溶液进行静电喷雾，即得到所述增韧剂。(4) Spraying: electrostatically spraying the polyurethane prepolymer solution to obtain the toughening agent.
对实施例1-5和对比例1-2进行拉伸强度、弯曲强度、抗冲击强度和阻燃性的测试，得到下表：The tensile strength, flexural strength, impact strength and flame retardancy of Examples 1-5 and Comparative Examples 1-2 were tested, and the following table was obtained:
由上表数据可知，本发明的阻燃耐老化塑料壳具有优良的机械性能，并且阻燃性能均能达到V0级别，符合高阻燃性需求；通过实施例1和对比例1的对比可知，本发明的增韧剂与常规的ACR和CPE相比，在增韧效果上是比较好的，并且可以显著提升塑料壳的弯曲强度和拉伸强度；通过对比例1和对比例2的对比可知，聚氨酯增韧剂对于弯曲强度和拉伸强度的提升是较为明显的，但是缺少纳米二氧化硅的刚性粒子增韧作用后，在抗冲击性能的提升上是不足的。As can be seen from the data in the above table, the flame-retardant and aging-resistant plastic shell of the present invention has excellent mechanical properties, and the flame-retardant properties can reach the V0 level, which meets the requirements of high flame retardancy; Compared with conventional ACR and CPE, the toughening agent of the present invention has better 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 , Polyurethane toughening agent has obvious improvement in bending strength and tensile strength, but lacking the toughening effect of rigid particles of nano-silica, it is insufficient in the improvement of impact resistance.
上述实施例为本发明较佳的实现方案，除此之外，本发明还可以其它方式实现，在不脱离本发明构思的前提下任何显而易见的替换均在本发明的保护范围之内。The above-mentioned embodiment is a preferred implementation scheme of the present invention. In addition, the present invention can also be implemented in other ways, and any obvious replacements are within the protection scope of the present invention without departing from the concept of the present invention.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811636916.0A CN109851946B (en) | 2018-12-29 | 2018-12-29 | Flame-retardant and aging-resistant plastic shell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811636916.0A CN109851946B (en) | 2018-12-29 | 2018-12-29 | Flame-retardant and aging-resistant plastic shell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109851946A CN109851946A (en) | 2019-06-07 |
| CN109851946B true CN109851946B (en) | 2020-10-23 |
Family
ID=66893231
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811636916.0A Active CN109851946B (en) | 2018-12-29 | 2018-12-29 | Flame-retardant and aging-resistant plastic shell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109851946B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03223338A (en) * | 1990-01-30 | 1991-10-02 | Shin Etsu Chem Co Ltd | Thermally shrinkable vinyl chloride resin film |
| CN104262671A (en) * | 2014-09-01 | 2015-01-07 | 中国林业科学研究院林产化学工业研究所 | Preparation method of hydroxyl-terminated polyurethane prepolymer toughening-modified phenolic foam |
| CN104861374A (en) * | 2014-12-29 | 2015-08-26 | 殷培花 | Polyvinyl chloride and polycarbonate alloy material with good flame retardancy |
| CN106496863A (en) * | 2016-11-07 | 2017-03-15 | 中广核三角洲（中山）高聚物有限公司 | A kind of mildew-proof flame retarded polrvinyl chloride sheath material of novel environment friendly |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7371275B2 (en) * | 2004-07-02 | 2008-05-13 | E.I. Du Pont De Nemours And Company | Titanium dioxide pigment and polymer compositions |
-
2018
- 2018-12-29 CN CN201811636916.0A patent/CN109851946B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03223338A (en) * | 1990-01-30 | 1991-10-02 | Shin Etsu Chem Co Ltd | Thermally shrinkable vinyl chloride resin film |
| CN104262671A (en) * | 2014-09-01 | 2015-01-07 | 中国林业科学研究院林产化学工业研究所 | Preparation method of hydroxyl-terminated polyurethane prepolymer toughening-modified phenolic foam |
| CN104861374A (en) * | 2014-12-29 | 2015-08-26 | 殷培花 | Polyvinyl chloride and polycarbonate alloy material with good flame retardancy |
| CN106496863A (en) * | 2016-11-07 | 2017-03-15 | 中广核三角洲（中山）高聚物有限公司 | A kind of mildew-proof flame retarded polrvinyl chloride sheath material of novel environment friendly |
Non-Patent Citations (2)
| Title |
|---|
| compatibility studies and characterisation of a PVC/NR blend system using NR/PU block copolymer;Nair, MNR等;《POLYMER BULLETIN》;20060430;第56卷(第6期);619-631 * |
| TPU与纳米SiO2共混增韧改性PET研究;崔建明等;《包装学报》;20120131;第4卷(第1期);29-33 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109851946A (en) | 2019-06-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109851946B (en) | Flame-retardant and aging-resistant plastic shell | |
| CN109627643B (en) | Insulating ageing-resistant plastic shell | |
| CN103525076B (en) | A kind of Halogen-free low-smoke flame-retardant TPE cable material | |
| WO2021129216A1 (en) | Pvc cable material and preparation method therefor | |
| CN103113692B (en) | The cold-resistant fire retarding antistatic polyvinyl chloride sheath material of a kind of coal mine cable | |
| CN106867080B (en) | A kind of rotational moulding special-purpose anti-flaming anti-static polyethylene composition and preparation method thereof | |
| CN114773826A (en) | Halogen-free flame-retardant water-mist-resistant polyurethane elastomer cable material and preparation method thereof | |
| CN109942890B (en) | Graphene-based antistatic agent with smoke suppression function and preparation method thereof | |
| CN110964307A (en) | Flame-retardant wear-resistant thermoplastic polyurethane composite material and preparation method thereof | |
| CN104356538B (en) | Flame-retardant smoke-eliminating polyvinyl chloride wire and cable material | |
| CN109988411B (en) | Flame-retardant smoke-suppression thermoplastic polyurethane antistatic composite material and preparation method thereof | |
| CN107090162A (en) | A kind of power distribution station electric power cabinet glass steel surface plate material and preparation method thereof | |
| CN103613913B (en) | A kind of Halogen-free flame-retardant thermoplastic polyester elastomer material and preparation method thereof | |
| CN113773628A (en) | Flame-retardant PC composition and preparation method thereof | |
| CN108148239A (en) | A kind of polyethylene sheath material for communication cable | |
| CN114479385A (en) | A conductive flame retardant biodegradable PBAT composite material and its preparation method and application | |
| CN106832556B (en) | Conveyor belt covering adhesive using synergistic flame retardant system and preparation method thereof | |
| CN103881182A (en) | Flame-retardant antistatic master batch used for polyethylene tubes, and its preparation method | |
| CN108929498B (en) | Polyamino cyclotriphosphazene synergistic flame-retardant smoke-suppressing PVC and preparation method thereof | |
| CN102391621A (en) | Novel halogen-free flame-retardant thermoplastic polyester elastomer (TPEE) and preparation method thereof | |
| CN108752727B (en) | Method for modifying flame-retardant ethylene-vinyl acetate copolymer by sol-gel method | |
| CN112851862A (en) | Environment-friendly flame-retardant plastic and preparation method thereof | |
| CN105440378A (en) | Insulating material for power distribution system | |
| CN114702729B (en) | High polymer material additive and application thereof in high polymer functional plastic | |
| CN105575456A (en) | Cold-resistant halogen-free flame-retardant copper composite cable material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |