CN103881370A - Flame-retardant PA6 material for corrugated pipe and preparation method thereof - Google Patents
Flame-retardant PA6 material for corrugated pipe and preparation method thereof Download PDFInfo
- Publication number
- CN103881370A CN103881370A CN201410084726.8A CN201410084726A CN103881370A CN 103881370 A CN103881370 A CN 103881370A CN 201410084726 A CN201410084726 A CN 201410084726A CN 103881370 A CN103881370 A CN 103881370A
- Authority
- CN
- China
- Prior art keywords
- flame
- proof
- corrugated tube
- retardant
- plastics
- 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.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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
- B29C48/92—Measuring, controlling or regulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/08—Organic materials containing halogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/88—Adding charges, i.e. additives
- B29B7/90—Fillers or reinforcements, e.g. fibres
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92561—Time, e.g. start, termination, duration or interruption
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92923—Calibration, after-treatment or cooling zone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses a flame-retardant PA6 material for a corrugated pipe and a preparation method thereof, relating to the technical field of materials. By adding a melt strength modifier and the like, the melt strength and impact toughness of the flame-retardant PA6 material are improved greatly, the defective rate of products is reduced, the rebound resilience of the corrugated pipe is enhanced, the application of the corrugated pipe is expanded, the produced flame-retardant PA6 has wider application and higher market competiveness. The flame-retardant PA6 material is safe and reliable to apply, and is particularly suitable for the fields of automobiles, building materials, household electrical appliances, office articles and the like.
Description
[technical field]
The present invention relates to material technology field, relate in particular to a kind of PA6 material and preparation method thereof, be specifically related to a kind of corrugated tube flame-proof PA 6 material and preparation method thereof.
[background technology]
Known, corrugated tube is mainly extruded and is formed by PE or PP or PA material, be widely used in the sleeve pipe of the aspect electric wire wire harness such as automobile, household electrical appliance, mechanical means, according to the environment of its use and condition, thereby select the corrugated tube that different base-materials are produced to use as the sleeve pipe of wire harness.
Due to the difference of PE, PP, PA material property, the performance of the corrugated tube of therefore producing is also respectively not quite similar, and the corrugated tube winter hardiness of wherein producing take PE as base-material is good, but poor heat resistance, rebound resilience is not good enough; Take PP as base-material, the corrugated tube winter hardiness of production, thermotolerance, rebound resilience, hardness are all in moderate, and therefore its purposes is the most extensive; The corrugated tube of producing take PA as base-material, has higher thermotolerance, oil-proofness and good rebound performance, the general environment that uses and oil resistant heat-resisting at needs.
Because corrugated tube is to extrude continuously machine-shaping, therefore the visco-elasticity to material and melt strength are had relatively high expectations, very difficult moulding, in recent years, along with automobile and household electrical appliance, to electrical equipment, fire-retardant requirement improves constantly, and therefore has higher fire-retardant requirement to using at the wire harness aspect automobile and household electrical appliances and sleeve pipe thereof.
And current fire-retardant PA fire retardant nearly 95～96% used is halogen containing flame-retardant, particularly the brominated flame-retardant efficiency take polybromodiphenyl ether and polybrominated biphenyl material as representative is high, consumption is few, performance impact to material is little, and moderate, its usefulness and production, non-other fire retardants of use cost ratio can be equal to, and therefore in China's electric series products for export, 70%～80% all use this based flame retardant.
In current fire-retardant PA industry, adopt following several systems:
(1), add halogenated flame retardant and inorganic combustion inhibitor, as antimonous oxide and aluminium hydroxide carry out composite.
(2), adopt organophosphorus, organic nitrogen-containing, organic siliceous system.
(3), inorganic fire-retarded system.
But no matter adopt above-mentioned which kind of system, due to adding of fire retardant, the mechanical properties decrease of system is very large, and especially very large on the impelling strength impact of material, the apparent mass of material reduces a lot in addition, the melt strength that the most important thing is material reduces, work range narrows, if do not carry out comprehensively modifying, is difficult to the fire-retardant corrugated tube of machine-shaping PA etc., therefore, research and develop the fire-retardant new technology of PA and just seem and be even more important, this is also those skilled in the art's long-term demand.
[summary of the invention]
For overcoming the deficiency existing in background technology, the invention provides a kind of corrugated tube flame-proof PA 6 material and preparation method thereof, the present invention improves and adds melt strength properties-correcting agent etc., the melt strength of flame-proof PA 6 material and the toughness of material are greatly improved, reduce the fraction defective of goods, improve the rebound resilience of corrugated tube, and then expanded the purposes of corrugated tube, made the flame-proof PA 6 of producing there is purposes and the stronger market competitiveness widely.
For realizing goal of the invention as above, the present invention adopts technical scheme as described below:
A kind of corrugated tube flame-proof PA 6 material, the component of described flame-proof PA 6 material comprises by weight percentage:
PA6 46～60%；
Halogenated flame retardant 18～22%;
Inorganic combustion inhibitor 2～7%;
Phosphorus flame retardant 3～5%;
Smoke suppressor 1～2.9%;
Melt strength improving agent 6～15%;
Suface-brightening agent 1～3% for plastics;
Hot oxidation inhibitor 0.1～2% for plastics;
Masterbatch 1～5% for plastics.
Described corrugated tube flame-proof PA 6 material, the medium-high viscosity material that the relative viscosity of described PA6 is 2～3, manufacturer is the PA6 that Yueyang Ba Ling petrochemical industry chemical industry and chemical fiber company produces, the trade mark is YH3000.
Described corrugated tube flame-proof PA 6 material, described halogenated flame retardant is the organic fire-retardant that contains elemental bromine, chlorine, described organic fire-retardant is perchloro-ring penta decane or two " hexachlorocyclopentadiene " cyclooctane or decabromodiphynly oxide or TDE or octabromodiphenyl ether or 1, any one in two " 2; 4; the 6-tribromophenoxy " ethane of 2-or two " tetrabromo phthalimide " ethane of 1,2-or tetrabromo-bisphenol or two kinds of combinations or two or more combinations.
Described corrugated tube flame-proof PA 6 material, described inorganic combustion inhibitor is antimonous oxide, and the effective content of described antimonous oxide is 99.5～100%, and whiteness is 95～100%, and particle diameter is 0.1～1um.
Described corrugated tube flame-proof PA 6 material, described phosphorus flame retardant is the mixture of one or both or three kinds in red phosphorus or polyphosphoric acid amine or phosphoric acid ester.
Described corrugated tube flame-proof PA 6 material, described smoke suppressor is PA6 fire-proof smoke suppressor, the combination of one or both that described PA6 fire-proof smoke suppressor is ZnO or ZnS.
Described corrugated tube flame-proof PA 6 material; described melt strength improving agent is any one or two or more the combination in plastic plasticizer or POE maleic anhydride grafts or EPDM maleic anhydride grafts, and described plastic plasticizer is one or both combination of aliphatic dihydroxy alcohol or aromatic series chlorosulfonylation thing.
Described corrugated tube flame-proof PA 6 material, described plastics are the combination of any one or two kinds in EBS or erucicamide with suface-brightening agent, described EBS is methylene bis stearylamide.
Described corrugated tube flame-proof PA 6 material, described plastics are the combination of phenolic antioxidant and phosphite ester kind antioxidant with hot oxidation inhibitor, hot oxidation inhibitor is that the ratio of phenolic antioxidant and phosphite ester kind antioxidant is 2:1.
A preparation method for flame-proof PA 6 material for corrugated tube, described method specifically comprises the steps:
The first step, the component of preparing flame-proof PA 6 material is prepared by proportioning after, in mixing machine, mix;
Second step, the compound that the first step is obtained carry out homogenizing and plasticate in twin screw extruder, be respectively 210～220 ℃, 236～240 ℃, 245～250 ℃, 245～250 ℃, 250～255 ℃, 255～258 ℃, 258～260 ℃ by charging opening to the temperature of the each heating zone of extrusion die, engine speed is 330～350rpm;
The 3rd step, the material that second step is obtained adopt cold drawn bar to be cut into particle, and carry out water-cooled, cross after vibratory screening apparatus and dry 1～4 hour at 90～130 ℃ with air flow dryer, then in post-type mixer, stir homogenizing after packing can obtain corrugated tube flame-proof PA 6 material.
Adopt technical scheme as above, the present invention has superiority as described below:
Flame-proof PA 6 material and preparation method thereof for a kind of corrugated tube of the present invention, the present invention is by adding melt strength properties-correcting agent etc., the melt strength of flame-proof PA 6 material and the toughness of material are greatly improved, reduce the fraction defective of goods, improve the rebound resilience of corrugated tube, and then expand the purposes of corrugated tube, make the flame-proof PA 6 of producing there is purposes and the stronger market competitiveness widely, application safety of the present invention is reliable, is specially adapted to the fields such as automobile, material of construction, household electrical appliance and office appliance.
[embodiment]
Can explain in more detail the present invention by the following examples, the present invention is not limited to the following examples;
A kind of corrugated tube flame-proof PA 6 material of the present invention, the component of described flame-proof PA 6 material comprises by weight percentage:
PA6 46～60%；
Halogenated flame retardant 18～22%;
Inorganic combustion inhibitor 2～7%;
Phosphorus flame retardant 3～5%;
Smoke suppressor 1～2.9%;
Melt strength improving agent 6～15%;
Suface-brightening agent 1～3% for plastics;
Hot oxidation inhibitor 0.1～2% for plastics;
Masterbatch 1～5% for plastics.
Further, the medium-high viscosity material that the relative viscosity of PA6 of the present invention is 2～3, described medium-high viscosity material is mainly in order to ensure extruding corrugated tube stable processing technique, can make final material modified intensity meet service requirements; The PA6 that preferred Yueyang Ba Ling petrochemical industry chemical industry and chemical fiber company of its manufacturer produces, the trade mark is YH3000; The present invention can also use the equivalent material of the same nature of other factory, as the equivalent material of the production such as Lihan Chemistry Co., Ltd., Nanjing, nylon factory of Heilongjiang Province.
Further, halogenated flame retardant of the present invention is the organic fire-retardant that contains elemental bromine, chlorine, described organic fire-retardant is perchloro-ring penta decane or two " hexachlorocyclopentadiene " cyclooctane or decabromodiphynly oxide or TDE or octabromodiphenyl ether or 1, two " 2; 4; the 6-tribromophenoxy " ethane or 1 of 2-, any one in two " tetrabromo phthalimide " ethane of 2-or tetrabromo-bisphenol or two kinds of combinations or two or more combinations, can guarantee that through the halogenated flame retardant of combination the flame retardant properties of material reaches UL-94 V0 level.
Further, inorganic combustion inhibitor of the present invention is antimonous oxide, and the effective content of described antimonous oxide is 99.5～100%, and whiteness is 95～100%, and particle diameter is 0.1～1um.
Further, phosphorus flame retardant of the present invention is the mixture of one or both or three kinds in red phosphorus or polyphosphoric acid amine or phosphoric acid ester, requires mixture will reach or meet general extrusion grade, and the good dispersiveness of tool.
Further, smoke suppressor of the present invention is PA6 fire-proof smoke suppressor, the combination of one or both that described PA6 fire-proof smoke suppressor is ZnO or ZnS, and its Main Function is to improve flame retardant properties, is issued to the fire-retardant requirement of V0 level in the lower situation of material cost.
Further; melt strength improving agent of the present invention is any one or two or more the combination in plastic plasticizer or POE maleic anhydride grafts or EPDM maleic anhydride grafts; described plastic plasticizer is one or both combination of aliphatic dihydroxy alcohol or aromatic series chlorosulfonylation thing; its Main Function is to improve material modified melt strength; make system in the situation that adding fire retardant; melt strength degree does not reduce, and finally contributes to improve the object of materials processing.
Further, plastics of the present invention are the combination of any one or two kinds in EBS or erucicamide with suface-brightening agent, and described EBS is methylene bis stearylamide; Its Main Function is to improve surface gloss.
Further, plastics of the present invention are the combination of phenolic antioxidant and phosphite ester kind antioxidant with hot oxidation inhibitor, and hot oxidation inhibitor is that the ratio of phenolic antioxidant and phosphite ester kind antioxidant is 2:1; Its Main Function is corrugated tube life-time service under comparatively high temps for a long time, and adding hot oxidation inhibitor is in order to improve the working life under material high temperature.
Further, plastics Masterbatch of the present invention is black Masterbatch, is characterized in that dyeing behavior is good, dispersiveness and good heat stability.
The preparation method of flame-proof PA 6 material for a kind of corrugated tube of the present invention, described method specifically comprises the steps:
The first step, the component of preparing flame-proof PA 6 material is prepared by proportioning after, in mixing machine, mix;
Second step, the compound that the first step is obtained carry out homogenizing and plasticate in twin screw extruder, be respectively 210～220 ℃, 236～240 ℃, 245～250 ℃, 245～250 ℃, 250～255 ℃, 255～258 ℃, 258～260 ℃ by charging opening to the temperature of the each heating zone of extrusion die, engine speed is 330～350rpm;
The 3rd step, the material that second step is obtained adopt cold drawn bar to be cut into particle, and carry out water-cooled, cross after vibratory screening apparatus and dry 1～4 hour at 90～130 ℃ with air flow dryer, then in post-type mixer, stir homogenizing after packing can obtain corrugated tube flame-proof PA 6 material.
The flame-proof PA 6 property indices contrast that corrugated tube of the present invention is combined into flame-proof PA 6 material and general applications fire retardant is as follows:
For convenience of description, corrugated tube of the present invention is labeled as to ZR1 with flame-proof PA 6, namely uses the routine of this area to describe replacement, the existing flame-proof PA 6 being combined into fire retardant is labeled as to ZR2, following table is the Data Comparison of ZR1 and ZR2 performance:
Data Comparison table
| Performance | Melt flow rate (MFR) (g/10min) | Melt strength (cN) | Normal temperature shock strength (KJ/m2) | Fire-retardant rank | Processibility |
| ZR1 | 2.6 | 23 | 15 | V0 | Good |
| ZR2 | 3 | 3.3 | V0 | Bad |
In conjunction with the Data Comparison of upper table, can clearly find out that ZR1 product of the present invention is obviously being better than ZR2 product aspect the index such as melt strength, shock strength, melt flow rate (MFR) is lower than ZR2 product, like this, corrugated tube processing characteristics is improved, substandard products reduce, easily produce, the rebound resilience of corrugated tube is also improved, and workman's production difficulty reduces, and makes the present invention meet the demand of flame-proof PA 6 in corrugated tube market.
Specific embodiments of the invention one, production code member ZR1-1:
ZR1-1 corrugated tube flame-proof PA 6 material of the present invention, is made up of following component by weight percentage: Yueyang Ba Ling petrochemical industry chemical industry and chemical fiber company produces PA6, trade mark YH3000, addition 46 %; Halogenated flame retardant TDE, addition 18 %; Inorganic combustion inhibitor antimonous oxide, addition 6%; Phosphorus flame retardant, addition 5%; Smoke suppressor, addition 2 %; Melt strength properties-correcting agent, addition 15%; Plastics suface-brightening agent, EBS(methylene bis stearylamide), addition 3%; The hot oxidation inhibitor of plastics, addition 0.4%; Plastics Masterbatch, addition 4.6%.
The ZR1-1 performance that more than formula is produced is as shown in the table:
| Performance | Melt flow rate (MFR) (g/10min) | Melt strength (cN) | Normal temperature shock strength (KJ/m2) | Fire-retardant rank | Processibility |
| ZR1-1 | 2.3 | 28 | 16.1 | V0 | Fine |
| ZR2 | 3 | 3.3 | V0 | Bad |
As can be seen from the above table: the ZR1-1 flame retardant products mechanical property excellence that embodiment mono-produces, melt strength shock strength is high, and melt flow rate (MFR) is low, and processing characteristics is fine, and product is compared or greater advantage.
Specific embodiments of the invention two, production code member ZR1-2:
ZR1-2 corrugated tube flame-proof PA 6 material of the present invention, is made up of following component by weight percentage: Yueyang Ba Ling petrochemical industry chemical industry and chemical fiber company produces PA6, trade mark YH3000, addition 52.6 %; Halogenated flame retardant TDE, addition 20.1%; Inorganic combustion inhibitor, antimonous oxide, addition 6.7%; Phosphorus flame retardant, addition 3.5%; Smoke suppressor, addition 1.5%; Melt strength properties-correcting agent, addition 12.5%; Plastics suface-brightening agent, EBS(methylene bis stearylamide), addition 1.5%; The hot oxidation inhibitor of plastics, addition 0.6%; Plastics Masterbatch, addition 1%.
The ZR1-2 performance that more than formula is produced is as shown in the table:
| Performance | Melt flow rate (MFR) (g/10min) | Melt strength (cN) | Normal temperature shock strength (KJ/m2) | Fire-retardant rank | Processibility |
| ZR1-2 | 3.6 | 22 | 10.3 | V0 | Good |
| ZR2 | 3 | 3.3 | V0 | Bad |
As can be seen from the above table: the ZR1-2 flame retardant products mechanical property excellence that embodiment bis-produces, melt strength shock strength is high, and melt flow rate (MFR) is low, good processability, product is compared or greater advantage.
Specific embodiments of the invention three, production code member ZR1-3:
ZR1-2 corrugated tube flame-proof PA 6 material of the present invention, is made up of following component by weight percentage: Yueyang Ba Ling petrochemical industry chemical industry and chemical fiber company produces PA6, trade mark YH3000, addition 58.6 %; Halogenated flame retardant TDE, addition 21%; Inorganic combustion inhibitor, antimonous oxide, addition 7%; Phosphorus flame retardant, addition 3%; Smoke suppressor, addition 1%; Melt strength properties-correcting agent, addition 6%; Plastics suface-brightening agent, EBS(methylene bis stearylamide), addition 1.6%; The hot oxidation inhibitor of plastics, addition 0.8%; Plastics Masterbatch, addition 1%.
The ZR1-3 performance that more than formula is produced is as shown in the table:
| Performance | Melt flow rate (MFR) (g/10min) | Melt strength (cN) | Normal temperature shock strength (KJ/m2) | Fire-retardant rank | Processibility |
| ZR1-3 | 4.0 | 16 | 7.6 | V0 | Better |
| ZR2 | 3 | 3.3 | V0 | Bad |
As can be seen from the above table: the ZR1-3 flame retardant products melt strength that embodiment tri-produces is higher, shock strength high energy meets use, and melt flow rate (MFR) is lower, and processibility is better, and product is compared and occupied some superiority.
The present invention is owing to having added melt strength properties-correcting agent, the melt strength of flame-proof PA 6 material and the toughness of material are greatly improved, reduce the fraction defective of goods, improve the rebound resilience of corrugated tube, expand the purposes of corrugated tube, make the flame-proof PA 6 of producing have purposes and the stronger market competitiveness widely, application safety of the present invention is reliable, is especially suitable for automobile, material of construction, household electrical appliance, office appliance etc.
Part not in the detailed description of the invention is prior art.
The embodiment selecting in this article for open object of the present invention, currently thinks suitablely, still, will be appreciated that, the present invention is intended to comprise that all belong to all changes and the improvement of the embodiment in this design and invention scope.
Claims (10)
1. a corrugated tube flame-proof PA 6 material, is characterized in that: the component of described flame-proof PA 6 material comprises by weight percentage:
PA6 46～60%；
Halogenated flame retardant 18～22%;
Inorganic combustion inhibitor 2～7%;
Phosphorus flame retardant 3～5%;
Smoke suppressor 1～2.9%;
Melt strength improving agent 6～15%;
Suface-brightening agent 1～3% for plastics;
Hot oxidation inhibitor 0.1～2% for plastics;
Masterbatch 1～5% for plastics.
2. corrugated tube according to claim 1 flame-proof PA 6 material, is characterized in that: the medium-high viscosity material that the relative viscosity of described PA6 is 2～3, and manufacturer is the PA6 that Yueyang Ba Ling petrochemical industry chemical industry and chemical fiber company produces, the trade mark is YH3000.
3. corrugated tube according to claim 1 flame-proof PA 6 material, it is characterized in that: described halogenated flame retardant is the organic fire-retardant that contains elemental bromine, chlorine, described organic fire-retardant is perchloro-ring penta decane or two " hexachlorocyclopentadiene " cyclooctane or decabromodiphynly oxide or TDE or octabromodiphenyl ether or 1, any one in two " 2; 4; the 6-tribromophenoxy " ethane of 2-or two " tetrabromo phthalimide " ethane of 1,2-or tetrabromo-bisphenol or two kinds of combinations or two or more combinations.
4. corrugated tube according to claim 1 flame-proof PA 6 material, is characterized in that: described inorganic combustion inhibitor is antimonous oxide, and the effective content of described antimonous oxide is 99.5～100%, and whiteness is 95～100%, and particle diameter is 0.1～1um.
5. corrugated tube according to claim 1 flame-proof PA 6 material, is characterized in that: described phosphorus flame retardant is the mixture of one or both or three kinds in red phosphorus or polyphosphoric acid amine or phosphoric acid ester.
6. corrugated tube according to claim 1 flame-proof PA 6 material, is characterized in that: described smoke suppressor is PA6 fire-proof smoke suppressor, the combination of one or both that described PA6 fire-proof smoke suppressor is ZnO or ZnS.
7. corrugated tube according to claim 1 flame-proof PA 6 material; it is characterized in that: described melt strength improving agent is any one or two or more the combination in plastic plasticizer or POE maleic anhydride grafts or EPDM maleic anhydride grafts, described plastic plasticizer is one or both combination of aliphatic dihydroxy alcohol or aromatic series chlorosulfonylation thing.
8. corrugated tube according to claim 1 flame-proof PA 6 material, is characterized in that: the agent of described plastics suface-brightening is the combination of any one or two kinds in EBS or erucicamide, and described EBS is methylene bis stearylamide.
9. corrugated tube according to claim 1 flame-proof PA 6 material, is characterized in that: described plastics are the combination of phenolic antioxidant and phosphite ester kind antioxidant with hot oxidation inhibitor, and hot oxidation inhibitor is that the ratio of phenolic antioxidant and phosphite ester kind antioxidant is 2:1.
10. the preparation method who utilizes a kind of corrugated tube flame-proof PA 6 material of a kind of corrugated tube flame-proof PA 6 material described in the arbitrary claim of claim 1～9, is characterized in that: described method specifically comprises the steps:
The first step, the component of preparing flame-proof PA 6 material is prepared by proportioning after, in mixing machine, mix;
Second step, the compound that the first step is obtained carry out homogenizing and plasticate in twin screw extruder, be respectively 210～220 ℃, 236～240 ℃, 245～250 ℃, 245～250 ℃, 250～255 ℃, 255～258 ℃, 258～260 ℃ by charging opening to the temperature of the each heating zone of extrusion die, engine speed is 330～350rpm;
The 3rd step, the material that second step is obtained adopt cold drawn bar to be cut into particle, and carry out water-cooled, cross after vibratory screening apparatus and dry 1～4 hour at 90～130 ℃ with air flow dryer, then in post-type mixer, stir homogenizing after packing can obtain corrugated tube flame-proof PA 6 material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410084726.8A CN103881370A (en) | 2014-03-10 | 2014-03-10 | Flame-retardant PA6 material for corrugated pipe and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410084726.8A CN103881370A (en) | 2014-03-10 | 2014-03-10 | Flame-retardant PA6 material for corrugated pipe and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103881370A true CN103881370A (en) | 2014-06-25 |
Family
ID=50950515
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410084726.8A Pending CN103881370A (en) | 2014-03-10 | 2014-03-10 | Flame-retardant PA6 material for corrugated pipe and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103881370A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104952533A (en) * | 2015-06-11 | 2015-09-30 | 深圳市骏鼎达科技有限公司 | Composite bushing, composite corrugated sleeve and manufacturing method of composite corrugated sleeve |
| CN106566232A (en) * | 2016-10-31 | 2017-04-19 | 无锡市永兴金属软管有限公司 | Chemical-corrosion- resistant PA corrugated pipe |
| CN106751798A (en) * | 2016-11-29 | 2017-05-31 | 株洲时代新材料科技股份有限公司 | One kind plasticising enhancing nylon material and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101374897A (en) * | 2006-01-26 | 2009-02-25 | 帝斯曼知识产权资产管理有限公司 | Flame retardant polyamide molding composition |
| CN102604377A (en) * | 2012-02-17 | 2012-07-25 | 金发科技股份有限公司 | Polyamide composition with flame retardance and thermoplasticity |
| CN102796367A (en) * | 2011-12-08 | 2012-11-28 | 上海耐特复合材料制品有限公司 | Flame-retardant nylon composite and preparation method and application thereof |
| CN103044896A (en) * | 2012-12-06 | 2013-04-17 | 上海日之升新技术发展有限公司 | High glow wire flame retarding reinforced PPO/PA alloy and preparation method thereof |
| CN103059346A (en) * | 2012-11-13 | 2013-04-24 | 金发科技股份有限公司 | Composite flame retardant, preparation method and application thereof |
| CN103102680A (en) * | 2013-02-20 | 2013-05-15 | 合肥杰事杰新材料股份有限公司 | Low-cost, flame retardant, wear-resistant and high-impact polyamide 6 composite material and preparation method |
| CN103351605A (en) * | 2013-06-29 | 2013-10-16 | 青岛共好检测技术有限公司 | Green environment-friendly flame-retardant nylon |
-
2014
- 2014-03-10 CN CN201410084726.8A patent/CN103881370A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101374897A (en) * | 2006-01-26 | 2009-02-25 | 帝斯曼知识产权资产管理有限公司 | Flame retardant polyamide molding composition |
| CN102796367A (en) * | 2011-12-08 | 2012-11-28 | 上海耐特复合材料制品有限公司 | Flame-retardant nylon composite and preparation method and application thereof |
| CN102604377A (en) * | 2012-02-17 | 2012-07-25 | 金发科技股份有限公司 | Polyamide composition with flame retardance and thermoplasticity |
| CN103059346A (en) * | 2012-11-13 | 2013-04-24 | 金发科技股份有限公司 | Composite flame retardant, preparation method and application thereof |
| CN103044896A (en) * | 2012-12-06 | 2013-04-17 | 上海日之升新技术发展有限公司 | High glow wire flame retarding reinforced PPO/PA alloy and preparation method thereof |
| CN103102680A (en) * | 2013-02-20 | 2013-05-15 | 合肥杰事杰新材料股份有限公司 | Low-cost, flame retardant, wear-resistant and high-impact polyamide 6 composite material and preparation method |
| CN103351605A (en) * | 2013-06-29 | 2013-10-16 | 青岛共好检测技术有限公司 | Green environment-friendly flame-retardant nylon |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104952533A (en) * | 2015-06-11 | 2015-09-30 | 深圳市骏鼎达科技有限公司 | Composite bushing, composite corrugated sleeve and manufacturing method of composite corrugated sleeve |
| CN106566232A (en) * | 2016-10-31 | 2017-04-19 | 无锡市永兴金属软管有限公司 | Chemical-corrosion- resistant PA corrugated pipe |
| CN106751798A (en) * | 2016-11-29 | 2017-05-31 | 株洲时代新材料科技股份有限公司 | One kind plasticising enhancing nylon material and preparation method thereof |
| CN106751798B (en) * | 2016-11-29 | 2019-06-21 | 株洲时代新材料科技股份有限公司 | A kind of plasticising enhancing nylon material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101824182B (en) | Halogen-free expansion type flame-retardant thermoplastic elastomer composition | |
| CN105623180B (en) | Halogen-free flame retardant thermoplastic elastomer material and preparation method thereof for electric wire | |
| CN101469089B (en) | Halogen-free polyvinyl composite for manufacturing pipes and manufacturing method thereof | |
| CN104854184B (en) | TPO fire-proof resin composition and shaped article | |
| CN105860412B (en) | Halogen-free flame retardant thermoplastic elastomer material and preparation method thereof for wire and cable | |
| CN101798460A (en) | Composite flame retardant glass fibre reinforced nylon 66 insulating strip and preparation method thereof | |
| CN102532693B (en) | High-performance low-smoke halogen-free flame-retardant polypropylene composite material and preparation method thereof | |
| CN103351525B (en) | A kind of high-glossiness flame-retardant polypropylene composite and preparation method thereof | |
| CN103849028A (en) | Antistatic flame-retardant reinforcing and toughening master batch | |
| CN103333469A (en) | Halogen-free flame-retardant PET (polyethylene terephthalate) composite material and preparation method thereof | |
| CN101469096A (en) | Flame-retardant polypropylene film material | |
| CN102993625A (en) | Halogen-free flame-retardant formaldehyde composite material with high CTI (comparative tracking index) and preparation method thereof | |
| CN109762292B (en) | ABS composition and preparation method thereof | |
| CN105111556A (en) | Thermoplastic elastomer used for electric car charging pile cable and preparing method of thermoplastic elastomer | |
| CN105088385A (en) | Flame-retarding polyamide fabric and preparation method thereof | |
| CN103756136A (en) | Halogen-free flame retardant polypropylene composition and preparation method thereof | |
| CN102424716A (en) | High-glow wire ignition temperature flame-retardant reinforced polybutylece terephthalate (PBT) material and preparation method thereof | |
| CN109957222A (en) | A kind of low precipitation flame retardant PBT composition | |
| CN104220514A (en) | Polyolefin intumescent phosphorous flame retardant system | |
| CN103881370A (en) | Flame-retardant PA6 material for corrugated pipe and preparation method thereof | |
| CN103740038A (en) | High-glossiness halogen-free flame-retardant ABS material and preparation method thereof | |
| CN103205017A (en) | Halogen-free fire retardant and preparation method of halogen-free fire-retardant PBT (polybutylece terephthalate) composite material | |
| CN107216650A (en) | A kind of long glass fiber reinforced halogen-free reinforced nylon compound and preparation method thereof | |
| CN102816405B (en) | Low-smoke halogen-free flame-retardant thermoplastic elastomer and preparation method thereof | |
| CN105670282A (en) | High-flame-retardancy halogen-free non-reinforced polyamide (PA) material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140625 |
|
| RJ01 | Rejection of invention patent application after publication |