CN101440211A - Environment-protecting flame-retardant composite filling reinforced nylon 66 and nylon 6 alloy material - Google Patents
Environment-protecting flame-retardant composite filling reinforced nylon 66 and nylon 6 alloy material Download PDFInfo
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- CN101440211A CN101440211A CNA2007101705599A CN200710170559A CN101440211A CN 101440211 A CN101440211 A CN 101440211A CN A2007101705599 A CNA2007101705599 A CN A2007101705599A CN 200710170559 A CN200710170559 A CN 200710170559A CN 101440211 A CN101440211 A CN 101440211A
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- nylon
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- alloy material
- retardant
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 40
- 229920002292 Nylon 6 Polymers 0.000 title claims abstract description 37
- 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 33
- 239000000956 alloy Substances 0.000 title claims abstract description 18
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 229920002302 Nylon 6,6 Polymers 0.000 title claims abstract description 12
- 238000011049 filling Methods 0.000 title claims description 14
- 239000003365 glass fiber Substances 0.000 claims abstract description 16
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000314 lubricant Substances 0.000 claims abstract description 7
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 5
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 5
- 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 abstract description 5
- 239000003112 inhibitor Substances 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- -1 polypropylene Polymers 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000005453 pelletization Methods 0.000 claims description 3
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 claims description 2
- 238000010559 graft polymerization reaction Methods 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 150000008301 phosphite esters Chemical class 0.000 claims description 2
- 229920006122 polyamide resin Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 abstract description 5
- 229920002647 polyamide Polymers 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000004677 Nylon Substances 0.000 abstract description 2
- 238000001746 injection moulding Methods 0.000 abstract description 2
- 229920001778 nylon Polymers 0.000 abstract description 2
- 229910045601 alloy Inorganic materials 0.000 abstract 2
- 238000012856 packing Methods 0.000 abstract 2
- 239000000463 material Substances 0.000 description 9
- BIEHXHIWQHAVFZ-UHFFFAOYSA-M bromoantimony Chemical compound [Sb]Br BIEHXHIWQHAVFZ-UHFFFAOYSA-M 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JTYRXXKXOULVAP-UHFFFAOYSA-N 1,2-dibromo-3-phenoxybenzene Chemical compound BrC1=CC=CC(OC=2C=CC=CC=2)=C1Br JTYRXXKXOULVAP-UHFFFAOYSA-N 0.000 description 1
- KTADSLDAUJLZGL-UHFFFAOYSA-N 1-bromo-2-phenylbenzene Chemical group BrC1=CC=CC=C1C1=CC=CC=C1 KTADSLDAUJLZGL-UHFFFAOYSA-N 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- LXWPJAGZRHTAOO-UHFFFAOYSA-N [Sb].[Br] Chemical compound [Sb].[Br] LXWPJAGZRHTAOO-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to an environment-friendly and flame-retardant composite packing reinforced nylon 66 and nylon 6 alloy material, which consists of a mixture. The environment-friendly and flame-retardant composite packing reinforced nylon 66 and nylon 6 alloy material comprises the following compositions by weight percentage: 15 to 52 percent of nylon 66, 15 to 52 percent of nylon 6, 12 to 25 percent of red phosphorus master batch, 1 to 10 percent of compatilizer, 10 to 20 percent of glass fibers, 10 to 20 percent of talc powder, 0 to 1 percent of antioxidant and 0 to 1 percent of lubricant. The flame-retardant polyamide alloy has high-efficiency flame retardant property, simultaneously greatly improves the rigidity and the heat resistance of the nylon and has good dimensional stability, belongs to an environment-friendly product, and is suitable for injection molding of various electronic and electric appliances and electrical household products with environment-friendly and flame-retardant requirements, and the flame retardant rating of the flame-retardant polyamide alloy can reach V0 rating of the UL94 standard.
Description
Technical field
The present invention relates to a kind of environment-protecting flame-retardant composite filling reinforced nylon 6 dragon 66 and nylon 6 alloy material, relate in particular to and a kind ofly be applicable to that injection moulding has the engineering materials goods of high electric insulation performance requriements and fire-retardant enhancing requirement, be suitable for the polyamide modified material of low-voltage vacuum contactor, isolating switch, low-tension switch, the electric element of thin-walled etc., belong to the modified polyamide technical field.
Technical background
Nylon 6 has good physics, mechanical property, tensile strength height for example, and excellent in abrasion resistance, shock resistance is good, and chemical-resistant resistance and oil-proofness are outstanding.Nylon 66 is even thermoplastic polyesters that a kind of molecular structure includes 6 symmetrical methylene radical, have high strength, wear-resisting, anti-solvent, advantage such as self lubricity is good and the use temperature scope is wide, be one of the widest engineering plastics of purposes, be widely used in various electronic electric equipments and household appliances.Because the present used fire retardant nearly 80% of fire-retardant nylon is a halogen containing flame-retardant, be that brominated flame-retardant efficient height, the consumption of representative is few particularly with polybromodiphenyl ether and polybrominated biphenyl material, performance impact to material is little, and it is moderate, its usefulness/price can be equal to than non-other fire retardants, so 70%～80% all uses this based flame retardant in the electric for export series products of China.But bromide fire retardant is subjected to the puzzlement of dioxin problem in recent years, use its (bromo-antimony system) fire-retardant macromolecular material the time can generate a large amount of flue dust and corrosive gases simultaneously, at present European Union and Japan this based flame retardant of use of putting into effect in succession that it is forbidden by decree in thermo-cracking and burning.European Union has risen on July 1st, 2006 and has implemented in full the ROHS instruction, and the electronic and electrical equipment that this decree requires to throw in European Union must not contain poly-dibromodiphenyl ether, poly-bromo biphenyl.
Summary of the invention
The object of the present invention is to provide a kind of environment-friendly high-efficiency flame retardant properties that has, satisfy environment-protecting flame-retardant composite filling reinforced nylon 6 dragon 66 and the nylon 6 alloy material and the preparation method of the ROHS of European Union command request simultaneously.
For realizing above purpose, technical scheme of the present invention provides a kind of environment-protecting flame-retardant composite filling reinforced nylon 6 dragon 66 and nylon 6 alloy material, is made up of a mixture, and its weight percent consists of:
Nylon 66 15-52%,
Nylon 6 15-52%,
Red phosphorus master batch 12-25%,
Compatilizer 1-10%,
Glass fibre 10-20%,
Talcum powder 10-20%,
Oxidation inhibitor 0-1%,
Lubricant 0-1%.
Wherein the relative viscosity of nylon 66 slice is 2.4-3.8PaS, and the relative viscosity of nylon 6 slice is 2.4-3.8PaS, and amido content is 30-90meq/kg, and content of carboxyl end group is 30-85meq/kg; The red phosphorus master batch is matrix with the polyamide resin, and red phosphorus content is the master batch of 30-65%; Compatilizer is the oligopolymer of the graft polymerization of polypropylene grafted unsaturated acid or acid anhydrides, is PP-g-MAH, and its melting index is 40-150g/10min, and percentage of grafting is 0.5-1%; Glass fibre is an alkali free glass fibre, and handle through silane coupling agent on its surface; Oxidation inhibitor is suffocated amine antioxidant, is 1098, or composite with phosphite ester kind antioxidant, can be 1098/168 (1:1); Described lubricant is MB-4.
Preparation technology of the present invention is:
The first step. weigh raw material by weight percentage;
Second step. remove glass fibre, other raw materials were put into high-speed mixer and mixing 2-5 minute;
The 3rd step. discharging;
The 4th step. raw materials mixed is added glass fibre screw rod machine extruding pelletization, and the rotating speed of screw rod machine is 180-600 rev/mins, and temperature is 235-270 ℃.
In combustion processes, not producing poisonous, obnoxious flavour with the fire-retardant polymeric amide of red phosphorus, is a class environmental-protection flame-retardant material, and the red phosphorus Flameproof polyamide can also farthest keep the electrical insulation capability of material.
Glass fibre and talcous adding can improve the resultant force of polymeric amide significantly, make material can reach the engineering level and use, and can also reduce cost.The adding of compatilizer can improve the adhesive capacity of polymkeric substance and red phosphorus master batch and talcum powder and glass fibre, and making respectively is on good terms obtains better dispersion effect, and performance is synergy better.
Oxidation inhibitor makes nylon 66 and nylon 6 have good processing stability in the course of processing, avoids color and luster, performance to change.
Advantage of the present invention is to adopt the environment friendly halogen-free fireproof agent, has abandoned traditional bromo-antimony flame-retardant system, has excellent flame-retardant, does not endanger environment and health of human body, belongs to environmentfriendly products.
Specific embodiments
Below in conjunction with embodiment, the present invention is described in further detail:
Embodiment 1 and 2: with nylon 66 and nylon 6 is matrix resin, and the red phosphorus master batch is a fire retardant, and compatilizer is PP-g-MAH, and oxidation inhibitor is 1098/168 (1:1); Lubricant is MB-4.
Proportioning 1-2 (weight %) (table 1)
| Material name | Proportioning 1 | Proportioning 2 |
| Nylon 66 | 29 | 17 |
| Nylon 6 | 26 | 29 |
| The red phosphorus master batch | 20 | 18 |
| PP-g-MAH | 4 | 5 |
| Alkali free glass fibre | 10 | 15 |
| Talcum powder | 10 | 15 |
| Lubricant | 0.5 | 0.5 |
| Oxidation inhibitor is 1098/168 (1:1) | 0.5 | 0.5 |
Said components was put into high-speed mixer and mixing 4 minutes in proportion except that glass fibre, add glass fibre screw extrusion press extruding pelletization then, the screw rod revolution is at 450 rev/mins, and each is distinguished processing temperature and is: (unit ℃)
| One district | Two districts | Three districts | Four districts | Five districts | Six districts | Seven districts | Eight districts | Nine districts | Ten districts |
| 240 | 245 | 250 | 255 | 255 | 255 | 255 | 255 | 255 | 255 |
A kind of environment-protecting flame-retardant composite filling reinforced nylon 6 dragon 66 and nylon 6 alloy material performance and traditional bromine antimony flame-retardant system contrast to embodiment 1 and embodiment 2 gained:
Mechanics Performance Testing is according to the ASTM standard, and flame retardant properties is tested according to the UL94 standard.
Test performance contrast (table 2)
| Project | Embodiment 1 | Embodiment 2 | Bromo-antimony flame-retardant system |
| Tensile strength (MPa) | 68.6 | 77.2 | 67.5 |
| Flexural strength (MPa) | 104.3 | 114.4 | 101.3 |
| Modulus in flexure (MPa) | 5831.2 | 6584.7 | 5279.2 |
| Shock strength (J/M) | 43.5 | 37.4 | 36.1 |
| Flame retardant resistance | VO | VO | VO |
Claims (8)
1. environment-protecting flame-retardant composite filling reinforced nylon 6 dragon 66 and nylon 6 alloy material is characterized in that, are mixed by following raw materials by weight percent and form:
Nylon 66 15-52%,
Nylon 6 15-52%,
Red phosphorus master batch 12-25%,
Compatilizer 1-10%,
Glass fibre 10-20%,
Talcum powder 10-20%,
Oxidation inhibitor 0-1%,
Lubricant 0-1%.
2. a kind of environment-protecting flame-retardant composite filling reinforced nylon 6 dragon 66 according to claim 1 and nylon 6 alloy material is characterized in that the relative viscosity of described nylon 66 slice is 2.4-3.8PaS, and end amido content is 30-90meq/kg.
3. a kind of environment-protecting flame-retardant composite filling reinforced nylon 6 dragon 66 according to claim 1 and nylon 6 alloy material is characterized in that described red phosphorus master batch is matrix with the polyamide resin, and red phosphorus content is the master batch of 30-65%.
4. a kind of environment-protecting flame-retardant composite filling reinforced nylon 6 dragon 66 according to claim 1 and nylon 6 alloy material, it is characterized in that, described compatilizer is the oligopolymer of the graft polymerization of polypropylene grafted unsaturated acid or acid anhydrides, be PP-g-MAH, its melting index is 40-150g/10min, and percentage of grafting is 0.5-1%.
5. a kind of environment-protecting flame-retardant composite filling reinforced nylon 6 dragon 66 according to claim 1 and nylon 6 alloy material is characterized in that described glass fibre is an alkali free glass fibre, and handle through silane coupling agent on its surface.
6. a kind of environment-protecting flame-retardant composite filling reinforced nylon 6 dragon 66 according to claim 1 and nylon 6 alloy material, it is characterized in that described oxidation inhibitor is suffocated amine antioxidant, is 1098, or composite with phosphite ester kind antioxidant, be 1098/168 of proportioning 1:1.
7. a kind of environment-protecting flame-retardant composite filling reinforced nylon 6 dragon 66 according to claim 1 and nylon 6 alloy material is characterized in that described lubricant is MB-4.
8. the preparation method of a kind of environment-protecting flame-retardant composite filling reinforced nylon 6 dragon 66 according to claim 1 and nylon 6 alloy material is characterized in that its preparation technology is:
The first step. weigh raw material by weight percentage;
Second step. remove glass fibre, other raw materials were put into high-speed mixer and mixing 2-5 minute;
The 3rd step. discharging;
The 4th step. raw materials mixed is added glass fibre extruding pelletization in the screw rod machine, and the rotating speed of screw rod machine is 180-600 rev/mins, and temperature is 235-270 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101705599A CN101440211A (en) | 2007-11-19 | 2007-11-19 | Environment-protecting flame-retardant composite filling reinforced nylon 66 and nylon 6 alloy material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101705599A CN101440211A (en) | 2007-11-19 | 2007-11-19 | Environment-protecting flame-retardant composite filling reinforced nylon 66 and nylon 6 alloy material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101440211A true CN101440211A (en) | 2009-05-27 |
Family
ID=40724831
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007101705599A Pending CN101440211A (en) | 2007-11-19 | 2007-11-19 | Environment-protecting flame-retardant composite filling reinforced nylon 66 and nylon 6 alloy material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101440211A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845221A (en) * | 2010-05-06 | 2010-09-29 | 浙江新力塑料股份有限公司 | Inflaming retarding reinforced plastic and preparation method thereof |
| CN102399430A (en) * | 2011-11-23 | 2012-04-04 | 上海日之升新技术发展有限公司 | Permanent antistatic PA6/PA66 alloy and preparation method thereof |
| CN102775776A (en) * | 2012-07-17 | 2012-11-14 | 上海日之升新技术发展有限公司 | Glass fiber reinforced polyamide 6/polyamide 66 (PA6/PA66) alloy composite and preparation method thereof |
| CN103788637A (en) * | 2014-02-26 | 2014-05-14 | 程六秀 | Composite material and preparation method thereof |
| CN106751776A (en) * | 2016-12-09 | 2017-05-31 | 宜春学院 | Composite of nano-nylon 6 and preparation method thereof |
| CN107523046A (en) * | 2016-06-21 | 2017-12-29 | 四川鑫达企业集团有限公司 | A kind of modification of nylon 3D consumptive material PP Pipe Compounds and preparation method thereof |
| CN110669333A (en) * | 2019-11-11 | 2020-01-10 | 江苏沃特新材料科技有限公司 | Flame-retardant nylon material and preparation method thereof |
-
2007
- 2007-11-19 CN CNA2007101705599A patent/CN101440211A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845221A (en) * | 2010-05-06 | 2010-09-29 | 浙江新力塑料股份有限公司 | Inflaming retarding reinforced plastic and preparation method thereof |
| CN101845221B (en) * | 2010-05-06 | 2012-05-30 | 浙江新力塑料股份有限公司 | Flame-retardant reinforced plastic and preparation method thereof |
| CN102399430A (en) * | 2011-11-23 | 2012-04-04 | 上海日之升新技术发展有限公司 | Permanent antistatic PA6/PA66 alloy and preparation method thereof |
| CN102399430B (en) * | 2011-11-23 | 2013-06-12 | 上海日之升新技术发展有限公司 | Permanently antistatic PA6/PA 66 (Polymide 6/Polymide 66) alloy and preparation method |
| CN102775776A (en) * | 2012-07-17 | 2012-11-14 | 上海日之升新技术发展有限公司 | Glass fiber reinforced polyamide 6/polyamide 66 (PA6/PA66) alloy composite and preparation method thereof |
| CN102775776B (en) * | 2012-07-17 | 2015-03-25 | 上海日之升新技术发展有限公司 | Glass fiber reinforced polyamide 6/polyamide 66 (PA6/PA66) alloy composite and preparation method thereof |
| CN103788637A (en) * | 2014-02-26 | 2014-05-14 | 程六秀 | Composite material and preparation method thereof |
| CN103788637B (en) * | 2014-02-26 | 2016-08-17 | 程六秀 | A kind of composite and preparation method thereof |
| CN107523046A (en) * | 2016-06-21 | 2017-12-29 | 四川鑫达企业集团有限公司 | A kind of modification of nylon 3D consumptive material PP Pipe Compounds and preparation method thereof |
| CN106751776A (en) * | 2016-12-09 | 2017-05-31 | 宜春学院 | Composite of nano-nylon 6 and preparation method thereof |
| CN110669333A (en) * | 2019-11-11 | 2020-01-10 | 江苏沃特新材料科技有限公司 | Flame-retardant nylon material and preparation method thereof |
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Open date: 20090527 |