CN100543081C - Polyformaldehyde resin of a kind of halogen-free environment-friendly flame-proof and preparation method thereof - Google Patents
Polyformaldehyde resin of a kind of halogen-free environment-friendly flame-proof and preparation method thereof Download PDFInfo
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- CN100543081C CN100543081C CNB200610157751XA CN200610157751A CN100543081C CN 100543081 C CN100543081 C CN 100543081C CN B200610157751X A CNB200610157751X A CN B200610157751XA CN 200610157751 A CN200610157751 A CN 200610157751A CN 100543081 C CN100543081 C CN 100543081C
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- tetramethylolmethane
- polyformaldehyde resin
- friendly flame
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- 229920006324 polyoxymethylene Polymers 0.000 title claims abstract description 48
- 229920005989 resin Polymers 0.000 title claims abstract description 17
- 239000011347 resin Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 26
- -1 polyoxymethylene Polymers 0.000 claims abstract description 19
- 229940059574 pentaerithrityl Drugs 0.000 claims abstract description 18
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 17
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims abstract description 15
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003112 inhibitor Substances 0.000 claims abstract description 13
- 238000005469 granulation Methods 0.000 claims abstract description 12
- 230000003179 granulation Effects 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000005303 weighing Methods 0.000 claims abstract description 3
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 6
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 4
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920001169 thermoplastic Polymers 0.000 claims description 3
- 239000004416 thermosoftening plastic Substances 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 abstract description 17
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 229910052736 halogen Inorganic materials 0.000 abstract description 4
- 150000002367 halogens Chemical class 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 229920000877 Melamine resin Polymers 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 16
- 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 description 10
- 239000011159 matrix material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002131 composite material Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005452 bending Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011236 particulate material Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 206010017472 Fumbling Diseases 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002929 anti-fatigue Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
Abstract
The present invention relates to polyformaldehyde resin of a kind of halogen-free environment-friendly flame-proof and preparation method thereof, it is mixed with by following proportion raw material: polyoxymethylene (POM) 40-62%, melamine cyanurate 12-25%, melamine phosphate 4-10%, tetramethylolmethane 2-8%, toughner 2-12%, oxidation inhibitor 0.1-1%, wear-resisting, anti-dripping agent 0.5-5%.This method comprises: take by weighing raw material by weight; With polyoxymethylene, toughner, wear-resisting, anti-dripping agent, oxidation inhibitor in moderate-speed mixers premix 2-3 minute, and then add melamine cyanurate, melamine phosphate, tetramethylolmethane mixing 5-10 minute; Raw materials mixed is placed dual-screw-stem machine, through melt extruding granulation.Polyformaldehyde resin of the present invention has that Halogen, security are good, environmental protection, fire-retardant performance.
Description
[technical field]
The present invention relates to the polyformaldehyde resin material, relate in particular to polyformaldehyde resin of a kind of halogen-free environment-friendly flame-proof that improves oxygen index and preparation method thereof.
[background technology]
Polyformaldehyde resin (polyformaldehyde is called for short POM), high comprehensive performance, easy to process, of many uses, and also raw material sources are abundant, develop into the important kind of general engineering plastic after coming out very soon.Its performance characteristics is: antifriction, wear-resisting, antifatigue and drug-resistant performance excellence, goods rigidity, elasticity and dimensional stability are good, be specially adapted to manufactured size requirement precision, cooperate demanding component.Polyoxymethylene is the present more satisfactory engineering plastics that can partly replace metallic substance.Yet, because its oxygen index extremely low (about 13%) that self molecular structure of polyoxymethylene is determined, this defective seriously limits its widespread use that can require high field at mechano-electronic, electrical equipment etc. to Flame Retardancy, therefore it is imperative polyoxymethylene to be carried out flame-retardant modified processing, and the affiliation that adds of fire retardant significantly reduces its physical and mechanical property, particularly former relatively weaker notch shock performance, so POM fire-retardant has sizable difficulty.At present, China is in the stage of fumbling in this field, there is not matured product to come out up to now as yet, again because the ROHS that European Union puts into effect recently instruction (TheRestriction of the use of certain Hazardous substances in Electnical andElectronic Equipment limit in electronic electric equipment and uses some objectionable impurities instruction) and WEEE instruct (instruction of Waste from Electrical and Electronic Equipment waste electronic andelectrical equipment) to advance the non-halogen process of material greatly, so halogen-free flameproof POM resin has great exploitation value.
For fire-retardant polyformaldehyde material of the prior art, the traditional bromine Sb system fire retardant and the adding of inorganic combustion inhibitor, poor with the polyoxymethylene consistency, bigger to the physical and mechanical property influence and the destruction of material, make material lose a lot of use value.
[summary of the invention]
The technical problem to be solved in the present invention provides polyformaldehyde resin of a kind of Halogen, safety, environmental protection and preparation method thereof.
Technical scheme of the present invention is:
A kind of polyformaldehyde resin of halogen-free environment-friendly flame-proof, it is mixed with by following proportion raw material:
Polyoxymethylene (POM) 40-62%
Melamine cyanurate 12-25%
Melamine phosphate 4-10%
Tetramethylolmethane 2-8%
Toughner 2-12%
Oxidation inhibitor 0.1-1%
Vinyl fluoride resinoid 0.5-5%.
Described toughner is thermoplastic elastomer.
Described thermoplastic elastomer is ethylene-propylene rubber(EPR) grafts or thermoplastic polyester.
Described oxidation inhibitor be triglycol two-3-(the 3-tertiary butyl-4 hydroxy-5-methyl base phenyl) vinyl cyanide, three (2, the 4-di-tert-butylphenol) phosphorous acid ester a kind of.
Described melamine cyanurate is 20%, and melamine phosphate is 8%, and tetramethylolmethane content is 4%, and the vinyl fluoride resinoid is 2%.
A kind of preparation method of polyformaldehyde resin of halogen-free environment-friendly flame-proof may further comprise the steps:
601, take by weighing raw material by weight: polyoxymethylene (POM) 40-62%, melamine cyanurate 12-25%, melamine phosphate 4-10%, tetramethylolmethane 2-8%, toughner 2-12%, oxidation inhibitor 0.1-1%, vinyl fluoride resinoid 0.5-5%;
602, with polyoxymethylene, toughner, vinyl fluoride resinoid, oxidation inhibitor in moderate-speed mixers premix 2-3 minute, and then add melamine cyanurate, melamine phosphate, tetramethylolmethane mixing 5-10 minute;
603, raw materials mixed is placed dual-screw-stem machine, through melt extruding, granulation, its technology is: twin screw one district temperature 150-160 ℃, two district temperature 160-170 ℃, three district temperature 165-175, four district temperature 170-180; Total residence time 1-2 minutes, melt pressure are 10-20MPa.
The invention has the beneficial effects as follows:
The present invention finds, by adding uric acid trimeric cyanamide, melamine phosphate, tetramethylolmethane three component composite flame-retardant agents, can improve the oxygen index of polyoxymethylene effectively, simultaneously because it is macromolecular material, good with the consistency of polyoxymethylene, thus little to the influence of its over-all properties, so prepared fire retardant material good combination property, and compliance with environmental protection requirements has a extensive future; The halogen-free environment-friendly flame-proof system that the present invention is made of melamine cyanurate, melamine phosphate, tetramethylolmethane in the halogen-free flameproof polyformaldehyde material makes that the physical and mechanical property of polyformaldehyde material is good, flame retardant properties is excellent; Auxiliary agent of the present invention as components such as melamine cyanurate, melamine phosphate, tetramethylolmethane, toughner and oxidation inhibitor, is cheap commercially available prod, and the production cost of material is lower; The preparation technology of halogen-free flameproof POM matrix material proposed by the invention is simple, cost is low.
[embodiment]
Below by embodiment the present invention is further set forth:
In implementing composite-material formula, polyoxymethylene is the copoly type polyoxymethylene, and fire retardant is melamine cyanurate, melamine phosphate, and for Italmatch company produces, trade names are MELANIC; Toughner is a kind of thermoplastic polyester (TPU), produces as Noveon company, and trade names are ES2388; Wear-resisting, anti-dripping agent is a polytetrafluoroethylene (PTFE), as Mitsubishi production, trade names A-3800; The oxidation inhibitor chemical name is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, produces as Ciba company, and trade names are Irganox 1010.
Embodiment 1
With weight ratio POM---61.8%, TPU---6%, PTFE---2%, 1010---0.2%, in moderate-speed mixers under room temperature state premix 2 minutes, and then add melamine cyanurate---18%, melamine phosphate---8%, tetramethylolmethane---4% mixed 5 minutes, then through melt extrude, granulation makes matrix material.155 ℃ of twin screw one district's temperature, 165 ℃ of two district's temperature, 170 ℃ of three district's temperature, 175 ℃ of four district's temperature; 1.5 minutes residence time, pressure is 12MPa.
Embodiment 2
With weight ratio POM---57.8%, TPU---6%, PTFE---2%, 1010---0.2%, in moderate-speed mixers under room temperature state premix 2 minutes, and then add melamine cyanurate---20%, melamine phosphate---9%, tetramethylolmethane---5% mixed 5 minutes, then through melt extrude, granulation makes matrix material.155 ℃ of twin screw one district's temperature, 165 ℃ of two district's temperature, 170 ℃ of three district's temperature, 175 ℃ of four district's temperature; 1.5 minutes residence time, pressure is 12MPa.
Embodiment 3
With weight ratio POM---53.8%, TPU---6%, PTFE---2%, 1010---0.2%, in moderate-speed mixers under room temperature state premix 2 minutes, and then add melamine cyanurate---22%, melamine phosphate---10%, tetramethylolmethane---6% mixed 5 minutes, then through melt extrude, granulation makes matrix material.155 ℃ of twin screw one district's temperature, 165 ℃ of two district's temperature, 170 ℃ of three district's temperature, 175 ℃ of four district's temperature; 1.5 minutes residence time, pressure is 12MPa.
Embodiment 4
With weight ratio POM---49.8%, TPU---6%, PTFE---2%, 1010---0.2%, in moderate-speed mixers under room temperature state premix 2 minutes, and then add melamine cyanurate---24%, melamine phosphate---11%, tetramethylolmethane---7% mixed 5 minutes, then through melt extrude, granulation makes matrix material.155 ℃ of twin screw one district's temperature, 165 ℃ of two district's temperature, 170 ℃ of three district's temperature, 175 ℃ of four district's temperature; 1.5 minutes residence time, pressure is 12MPa.
Embodiment 5
With weight ratio POM---45.8%, TPU---6%, PTFE---2%, 1010---0.2%, in moderate-speed mixers under room temperature state premix 2 minutes, and then add melamine cyanurate---26%, melamine phosphate---12%, tetramethylolmethane---8% mixed 5 minutes, then through melt extrude, granulation makes matrix material.155 ℃ of twin screw one district's temperature, 165 ℃ of two district's temperature, 170 ℃ of three district's temperature, 175 ℃ of four district's temperature; 1.5 minutes residence time, pressure is 12MPa.
Embodiment 6
With weight ratio POM---41.8%, TPU---6%, PTFE---2%, 1010---0.2%, in moderate-speed mixers under room temperature state premix 2 minutes, and then add melamine cyanurate---28%, melamine phosphate---13%, tetramethylolmethane---9% mixed 5 minutes, then through melt extrude, granulation makes matrix material.155 ℃ of twin screw one district's temperature, 165 ℃ of two district's temperature, 170 ℃ of three district's temperature, 175 ℃ of four district's temperature; 1.5 minutes residence time, pressure is 12MPa.
It is pointed out that in the above-mentioned example that the time range of premix can be 2-3 minute in moderate-speed mixers, and then add melamine cyanurate, melamine phosphate, tetramethylolmethane mixing 5-10 minute; In dual-screw-stem machine, its technology also can for: twin screw one district temperature 150-160 ℃, two district temperature 160-170 ℃, three district temperature 165-175, four district temperature 170-180; Total residence time 1-2 minutes, melt pressure are 10-20MPa.
Comparative Examples 1
With weight ratio POM---59.8%, TPU---6%, PTFE---2%, 1010---0.2%, in moderate-speed mixers under room temperature state premix 2 minutes, and then adding melamine cyanurate---22%, melamine phosphate---10% mixed 5 minutes, then through melt extrude, granulation makes matrix material.155 ℃ of twin screw one district's temperature, 165 ℃ of two district's temperature, 170 ℃ of three district's temperature, 175 ℃ of four district's temperature; 1.5 minutes residence time, pressure is 12MPa.
Comparative Examples 2
With weight ratio POM---55.8%, TPU---6%, 1010---0.2%, in moderate-speed mixers under room temperature state premix 2 minutes, and then adding melamine cyanurate---22%, melamine phosphate---10%, tetramethylolmethane---6% mixed 5 minutes, then through melt extrude, granulation makes matrix material.155 ℃ of twin screw one district's temperature, 165 ℃ of two district's temperature, 170 ℃ of three district's temperature, 175 ℃ of four district's temperature; 1.5 minutes residence time, pressure is 12MPa.
Performance evaluation mode and implementation standard:
With the particulate material of finishing granulation as stated above in 80 ℃ convection oven dry 3-6 hours in advance, and then the particulate material that drying is good carried out the injection molding sample preparation on injection machine, and the injection mold temperature control is about 100 ℃.
The tensile strength test is undertaken by IS0527-2, and specimen size is 150 * 10 * 4mm, and draw speed is 50mm/min; The bending property test is undertaken by ISO 178, and specimen size is 80 * 10 * 4, and rate of bending is 2mm/min, and span is 64mm; Simple beam impact strength is undertaken by ISO 179, and specimen size is 55 * 6 * 4mm, and notch size is 1/3rd of a sample thickness; Flame retardant properties is undertaken by the UL94 method, and batten thickness is approximately 1.5mm.
Comprehensive mechanical property is passed judgment on by the numerical value of tensile strength, elongation at break, modulus in flexure and the shock strength of test gained; The flame retardant properties of material is passed judgment on by the standard of UL94.
The prescription of embodiment 1-6 and Comparative Examples 1-2 and Mechanics Performance Testing the results are shown in Table 1 and table 2;
The prescription of table 1 embodiment 1-6 and material property table
| Form | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| POM(％) | 61.8 | 57.8 | 53.8 | 49.8 | 45.8 | 41.8 |
| MCA(％) | 18 | 20 | 22 | 24 | 26 | 28 |
| MP(％) | 8 | 9 | 10 | 11 | 12 | 13 |
| Tetramethylolmethane (%) | 4 | 5 | 6 | 7 | 8 | 9 |
| TPU(％) | 6 | 6 | 6 | 6 | 6 | 6 |
| 1010(％) | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| PTFE(％) | 2 | 2 | 2 | 2 | 2 | 2 |
| Notched Izod impact strength (KJ/M2) | 15 | 14.2 | 13.8 | 12.6 | 10 | 7 |
| Tensile strength (Mpa) | 50 | 51 | 48 | 46 | 38 | 37 |
| Elongation at break (%) | 20 | 18 | 15 | 12 | 9 | 10 |
| Modulus in flexure (Mpa) | 1800 | 1820 | 1780 | 1700 | 1700 | 1680 |
| Flame retardant resistance (UL94) | V2 | V2 | V0 | V0 | V0 | V0 |
The prescription of table 2 Comparative Examples 1-2 and material property table
| Form | Comparative Examples 1 | Comparative Examples 2 |
| POM(％) | 59.8 | 55.8 |
| MCA(％) | 22 | 22 |
| MP(％) | 10 | 10 |
| Tetramethylolmethane (%) | ——— | 4 |
| TPU(％) | 6 | 6 |
| PTFE(％) | 2 | ——— |
| 1010 | 0.2 | 0.3 |
| Notched Izod impact strength (KJ/M2) | 16 | 15 |
| Tensile strength (Mpa) | 55 | 45 |
| Elongation at break (%) | 20 | 12 |
| Modulus in flexure (Mpa) | 1800 | 1750 |
| Flame retardant resistance (UL94) | HB | V2 |
Every performance analysis by table 1 embodiment 1-6 and table 2 Comparative Examples 1-2 as can be known, the comprehensive mechanical property of halogen-free flameproof polyformaldehyde composite material is better, and its flame retardant properties has reached the standard of UL94V0.And from every performance data of table 1 embodiment 1-6, three kinds of components of Halogen composite flame retardant system lack wherein that a kind ofly all can't reach flame-retardant V 0-stage, and the drippage problem of the adding of anti-drippage, anti-wear agent can improve material combustion effectively the time.And addition too much can influence the comprehensive physical and mechanical property of material.The MCA addition is 20%, and MP content is 8%, and tetramethylolmethane content is 4%, and anti-drippage, anti-wear agent are that 2% o'clock comprehensive mechanical performance and flame retardant resistance are all better, the composite material combination property excellence of handling through above modification.
The characteristics such as the oxygen index (OI) of polyformaldehyde material of the present invention effectively improves, and it has, and preparation technology is simple, cost is moderate, every physical and chemical performance excellent, fire resistance is good can be used for the technical fields such as auto parts machinery, automobile, electronics industry.
Claims (6)
1, a kind of polyformaldehyde resin of halogen-free environment-friendly flame-proof is characterized in that, it is mixed with by following proportion raw material:
Polyoxymethylene 40-62%
Melamine cyanurate 12-25%
Melamine phosphate 4-10%
Tetramethylolmethane 2-8%
Toughner 2-12%
Oxidation inhibitor 0.1-1%
Vinyl fluoride resinoid 0.5-5%.
2, the polyformaldehyde resin of a kind of halogen-free environment-friendly flame-proof according to claim 1 is characterized in that: described toughner is thermoplastic elastomer.
3, the polyformaldehyde resin of a kind of halogen-free environment-friendly flame-proof according to claim 2 is characterized in that: described thermoplastic elastomer is ethylene-propylene rubber(EPR) grafts or thermoplastic polyester.
4, the polyformaldehyde resin of a kind of halogen-free environment-friendly flame-proof according to claim 1 is characterized in that: described oxidation inhibitor be triglycol two-3-(the 3-tertiary butyl-4 hydroxy-5-methyl base phenyl) vinyl cyanide, three (2, the 4-di-tert-butylphenol) phosphorous acid ester a kind of.
5, the polyformaldehyde resin of a kind of halogen-free environment-friendly flame-proof according to claim 1 is characterized in that: described melamine cyanurate is 20%, and melamine phosphate is 8%, and tetramethylolmethane content is 4%, and the vinyl fluoride resinoid is 2%.
6, a kind of preparation method of polyformaldehyde resin of halogen-free environment-friendly flame-proof is characterized in that, may further comprise the steps:
601, take by weighing raw material by weight: polyoxymethylene (POM) 40 one 62%, melamine cyanurate 12-25%, melamine phosphate 4-10%, tetramethylolmethane 2-8%, toughner 2-12%, oxidation inhibitor 0.1-1%, vinyl fluoride resinoid 0.5-5%;
602, with polyoxymethylene, toughner, vinyl fluoride resinoid, oxidation inhibitor in moderate-speed mixers premix 2-3 minute, and then add melamine cyanurate, melamine phosphate, tetramethylolmethane mixing 5-10 minute;
603, raw materials mixed is placed dual-screw-stem machine, through melt extruding, granulation, its technology is: twin screw one district temperature 150-160 ℃, two district temperature 160-170 ℃, three district temperature 165-175 ℃, four district temperature 170-180 ℃; Total residence time 1-2 minutes, melt pressure are 10-20MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610157751XA CN100543081C (en) | 2006-12-28 | 2006-12-28 | Polyformaldehyde resin of a kind of halogen-free environment-friendly flame-proof and preparation method thereof |
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| CNB200610157751XA CN100543081C (en) | 2006-12-28 | 2006-12-28 | Polyformaldehyde resin of a kind of halogen-free environment-friendly flame-proof and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113490705A (en) * | 2018-12-07 | 2021-10-08 | 乐金华奥斯有限公司 | Thermosetting foam, method for producing same, and heat insulating material comprising same |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329471B (en) * | 2011-06-24 | 2013-01-16 | 深圳市科聚新材料有限公司 | Fiberglass-reinforced polyformaldehyde material and preparation method thereof |
| CN102585329A (en) * | 2012-01-16 | 2012-07-18 | 长园集团股份有限公司 | Halogen-free non-red-phosphorus flame-retardant thermal shrinkable tube and preparation method thereof |
| CN102993626A (en) * | 2012-08-22 | 2013-03-27 | 广东威林工程塑料有限公司 | Anti-inflaming reinforced and toughened POM (polyformaldehyde) composite and preparation method thereof |
| CN102875846B (en) * | 2012-10-25 | 2013-09-04 | 上海韬鸿化工科技有限公司 | Composite environmental-friendly flame retardant for POM (polyoxymethylene) and POM flame-retardant plastic |
| CN103194034A (en) * | 2013-04-10 | 2013-07-10 | 苏州旭光聚合物有限公司 | Reinforced flame-retardant POM (Polyoxymethylene) material and preparation method thereof |
| CN103304954B (en) * | 2013-05-10 | 2014-11-05 | 太仓市天合新材料科技有限公司 | Polyoxymethylene plastic plate |
| CN106189055A (en) * | 2016-08-24 | 2016-12-07 | 桂林浩新科技服务有限公司 | A kind of polyoxymethylene resin composition |
| CN106189056A (en) * | 2016-08-24 | 2016-12-07 | 桂林浩新科技服务有限公司 | The aldehyde resin composition that a kind of high bonding strength is poly- |
| CN106221118A (en) * | 2016-08-24 | 2016-12-14 | 桂林浩新科技服务有限公司 | A kind of polyoxymethylene resin composition of high ductibility |
-
2006
- 2006-12-28 CN CNB200610157751XA patent/CN100543081C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 聚甲醛阻燃的研究. 刘鹏波，徐闻，李英杰.高分子材料科学与工程，第20卷第6期. 2004 |
| 聚甲醛阻燃的研究. 刘鹏波，徐闻，李英杰.高分子材料科学与工程，第20卷第6期. 2004 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113490705A (en) * | 2018-12-07 | 2021-10-08 | 乐金华奥斯有限公司 | Thermosetting foam, method for producing same, and heat insulating material comprising same |
| CN113490705B (en) * | 2018-12-07 | 2023-03-03 | 乐金华奥斯有限公司 | Thermosetting foam, method for producing same, and heat insulating material comprising same |
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| CN1995130A (en) | 2007-07-11 |
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