CN104072981A - Halogen-free flame retardant polyamide material and preparation method thereof - Google Patents
Halogen-free flame retardant polyamide material and preparation method thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 81
- 239000000463 material Substances 0.000 title claims abstract description 58
- 239000004952 Polyamide Substances 0.000 title claims abstract description 55
- 229920002647 polyamide Polymers 0.000 title claims abstract description 55
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims description 7
- 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 claims abstract description 51
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 24
- 239000010703 silicon Substances 0.000 claims abstract description 24
- 229940071182 stannate Drugs 0.000 claims abstract description 19
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical group [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000003607 modifier Substances 0.000 claims abstract description 13
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 13
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004677 Nylon Substances 0.000 claims description 11
- 229920001778 nylon Polymers 0.000 claims description 11
- 229920002292 Nylon 6 Polymers 0.000 claims description 10
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000005520 cutting process Methods 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 9
- 239000003365 glass fiber Substances 0.000 claims description 9
- 239000000314 lubricant Substances 0.000 claims description 9
- 229920006119 nylon 10T Polymers 0.000 claims description 9
- -1 polyparaphenylene terephthalamide Polymers 0.000 claims description 8
- 229920000571 Nylon 11 Polymers 0.000 claims description 5
- 229920000299 Nylon 12 Polymers 0.000 claims description 5
- 229920003189 Nylon 4,6 Polymers 0.000 claims description 5
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920000393 Nylon 6/6T Polymers 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 229940018564 m-phenylenediamine Drugs 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 10
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 7
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 7
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 7
- 238000005452 bending Methods 0.000 description 5
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 4
- LXWPJAGZRHTAOO-UHFFFAOYSA-N [Sb].[Br] Chemical compound [Sb].[Br] LXWPJAGZRHTAOO-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 2
- 229920000572 Nylon 6/12 Polymers 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920006123 polyhexamethylene isophthalamide Polymers 0.000 description 2
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
Classifications
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- 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
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
- B29B9/14—Making granules characterised by structure or composition fibre-reinforced
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- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
-
- 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
- B29B7/58—Component parts, details or accessories; Auxiliary operations
- B29B7/72—Measuring, controlling or regulating
-
- 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
- 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
- B29C48/25—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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- 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
-
- 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
-
- 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
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- 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
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- 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
- B29C2948/92009—Measured parameter
- B29C2948/92266—Mechanical properties
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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Abstract
The invention discloses a halogen-free flame retardant polyamide material which is mainly prepared from the following components in parts by weight: 40-72 parts of polyamide, 8-15 parts of a halogen-free flame retardant, 3-9 parts of a flame retardant synergist, 0.5-2 parts of a processing aid and 0-40 parts of a reinforcing modifier, wherein the halogen-free flame retardant is hypophosphite and the flame retardant synergist is silicon stannate with the silicon content being 30-60%. By adding the flame retardant synergist silicon stannate to reduce the use level of the halogen-free flame retardant hypophosphite, the flame retardant performance and the mechanical property are more excellent than those of a flame retardant material without adding silicon stannate, so that the cost is lowered. For the flame retardant material without adding silicon stannate, in spite of high content of the halogen-free flame retardant hypophosphite, the GWIT (Glow Wire Ignition Temperature) still cannot reach 960 DEG C. By adding silicon stannate, the GWIT of the material is greatly enhanced and substantially reaches 960 DEG C.
Description
Technical Field
The invention relates to a halogen-free flame-retardant polyamide material and a preparation method thereof.
Background
The polyamide resin has the excellent characteristics of wear resistance, oil resistance, impact resistance, fatigue resistance, corrosion resistance, excellent self-lubricating property, small friction coefficient and the like, and is very wide in application. The flame-retardant modified polyamide has outstanding mechanical properties and excellent flame-retardant property, and is widely applied to the fields of electronics, electrics, transportation, electric tools, mechanical parts and the like. The bromine-antimony flame retardant modification technology is a common technology for flame retardant modified polyamide because of small addition amount of flame retardant and high flame retardant efficiency, but the bromine-antimony flame retardant has the defect of high toxicity. In recent years, with the increasing demand of people for environmental protection, the market demand for non-halogenation of flame retardant materials is increasing, and halogen-free flame retardant modified polyamide will become the mainstream technology of flame retardant modified polyamide in the foreseeable future. Compared with a bromine-antimony flame retardant system, the halogen-free flame retardant modified polyamide has low toxicity and is environment-friendly, but has obvious defects, for example, the halogen-free flame retardant has large addition amount, so that the mechanical property is obviously reduced, the cost is high, and the defect of low Glow Wire Ignition Temperature (GWIT) exists, so that the application of the halogen-free flame retardant modified polyamide in the fields of low-voltage electricity and the like with high GWIT requirements is limited.
Disclosure of Invention
The invention aims to provide a halogen-free flame-retardant polyamide material and a preparation method thereof, the halogen-free flame-retardant polyamide material reduces the using amount of a halogen-free flame retardant, maintains the mechanical properties of the material, reduces the material cost and improves the ignition temperature of a glow wire.
In order to achieve the purpose, the invention provides a halogen-free flame-retardant polyamide material, which comprises the following main components in parts by weight:
40-72 parts of polyamide, namely,
8-15 parts of a halogen-free flame retardant,
3-9 parts of a flame-retardant synergist,
0.5-2 parts of a processing aid,
0-40 parts of a reinforcing modifier;
wherein,
the halogen-free flame retardant is hypophosphite;
the flame-retardant synergist is silicon stannate with silicon content of 30-60%.
Preferably, the polyamide is one of the following polyamides or a mixture of any several of the following polyamides: polycaprolactam (nylon 6), polytetramethyleneadipamide (nylon 46), polyhexamethyleneadipamide (nylon 66), polyhexamethylenesebacamide (nylon 610), polyhexamethylenedodecamide (nylon 612), henamethylenediamide (nylon 116), polyundecanolactam (nylon 11), polydodecanolactam (nylon 12), polyparaphenylene terephthalamide, polyisophthaloyl isophthalamide, polytrimethylhexamethylenediamine terephthalamide, polyhexamethyleneisophthalamide (nylon 6I), polytrimethylmethylenediamine nonapthalate (nylon 9T), polyhexamethyleneterephthalamide (nylon 6T), nylon 10T, nylon 12T, nylon 10T/1012, nylon 6/6T, nylon 46/10T, and polydodecanedioic bis (4-aminocyclohexyl) methane (nylon PACM 12).
Preferably, the processing aid is a lubricant and an antioxidant.
Preferably, the reinforcing modifier is alkali-free glass fiber.
Preferably, the polyamide is polycaprolactam (nylon 6) and/or polyhexamethylene adipamide (nylon 66).
The invention also provides a preparation method of the halogen-free flame-retardant polyamide material, which comprises the following steps:
1) preparing materials according to the parts by weight;
2) firstly, mixing polyamide and a processing aid, and then adding a halogen-free flame retardant and a flame-retardant synergist for mixing to obtain a mixed material;
3) adding the mixed material from a main feeding port of a double-screw extruder, adding the reinforcing modifier from a side feeding port of the extruder, and performing melt extrusion, cooling and grain cutting to obtain the halogen-free flame-retardant polyamide material; wherein the temperatures of the twin-screw extruder from the feeding section to the head are respectively as follows: 210-240 ℃, 230-275 ℃, 245-280 ℃, 245-275 ℃, 240-270 ℃, 235-265 ℃, 230-260 ℃ and 235-270 ℃ of the die head.
The invention has the advantages and beneficial effects that: the halogen-free flame retardant polyamide material and the preparation method thereof are provided, the using amount of hypophosphite of a halogen-free flame retardant is reduced by adding a flame retardant synergist of the silicon stannate, the flame retardant property and the mechanical property are more excellent than those of a flame retardant material without the silicon stannate, and the cost is reduced; although the hypophosphite content of the flame retardant is high, the GWIT of the flame retardant is still not 960 ℃, and the silicon stannate is added, so that the GWIT (glow wire ignition temperature) of the material is greatly improved and can basically reach 960 ℃.
Detailed Description
The following further describes embodiments of the present invention with reference to examples. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
The raw materials used in the embodiments of the invention are:
PA66 was purchased from Hill-Sharpe Marie GmbH, model EPR24, and had a relative viscosity of 2.45. + -. 0.03.
PA6 was purchased from Rimefural, Jiangsu, model M1013B, and had a relative viscosity of 2.43. + -. 0.03.
Hypophosphite was purchased from clariant corporation, model OP1312 (silicon content 30% -60%).
The alkali-free glass fiber is ECS301HP from Shanghai Langyu industries, Ltd.
Example 1
1) Firstly, 40 parts of polyamide EPR24, 1 part of lubricant ethylene bis stearamide EBS (P-130), 0.5 part of antioxidant 1098 and 0.5 part of antioxidant 168 are mixed, and then 15 parts of hypophosphite OP1312 and 3 parts of silicon stannate are added and mixed to obtain a mixed material;
2) adding the mixed material from a main feeding port of a double-screw extruder, adding 40 parts of the alkali-free glass fiber ECS301HP serving as the reinforcing modifier from a side feeding port of the extruder, and performing melt extrusion, cooling and grain cutting to obtain the flame-retardant polyamide material; wherein the temperatures of the twin-screw extruder from the feed zone to the head are 240 ℃, 275 ℃, 280 ℃, 275 ℃, 270 ℃, 265 ℃ and 260 ℃ respectively, and the die temperature is 270 ℃.
Example 2
1) Firstly, 58 parts of polyamide M1013B, 0.2 part of lubricant ethylene bis stearamide EBS (P-130), 0.1 part of antioxidant 1098 and 0.2 part of antioxidant 168 are mixed, then 10 parts of halogen-free flame retardant hypophosphite OP1312 and 6.5 parts of silicon stannate are added and mixed, and the materials are mixed;
2) adding the mixed material from a main feed of a double-screw extruder, adding 25 parts of the alkali-free glass fiber ECS301HP serving as the reinforcing modifier from a feeding port of the extruder, and performing melt extrusion, cooling and grain cutting to obtain the flame-retardant polyamide material; wherein the temperature of the double-screw extruder from the feeding section to the machine head is respectively as follows: 210 ℃, 230 ℃, 245 ℃, 240 ℃, 235 ℃, 230 ℃ and the die temperature is 235 ℃.
Example 3
1) Firstly, 40 parts of polyamide EPR24, 32 parts of M1013B, 0.4 part of lubricant ethylene bis stearamide EBS (P-130), 0.3 part of antioxidant 1098 and 0.3 part of antioxidant 168 are mixed, and then 15 parts of halogen-free flame retardant hypophosphite OP1312 and 9 parts of silicon stannate are added and mixed to obtain a mixed material;
2) adding the mixed material from a main feed of a double-screw extruder, and performing melt extrusion, cooling and cutting to obtain the flame-retardant polyamide material; wherein the temperature of the double-screw extruder from the feeding section to the machine head is respectively as follows: 220 ℃, 260 ℃, 265 ℃, 260 ℃, 255 ℃, 260 ℃ and the die temperature is 260 ℃.
Example 4
1) Firstly, 10 parts of polyamide EPR24, 44 parts of M1013B, 0.5 part of lubricant ethylene bis stearamide EBS (P-130), 0.2 part of antioxidant 1098 and 0.3 part of antioxidant 168 are mixed, and then 8 parts of halogen-free flame retardant hypophosphite OP1312 and 7 parts of silicon stannate are added and mixed to obtain a mixed material;
2) adding the mixed material from a main feed of a double-screw extruder, adding 30 parts of the alkali-free glass fiber ECS301HP serving as the reinforcing modifier from a measuring feed port of the extruder, and performing melt extrusion, cooling and cutting to obtain the flame-retardant polyamide material; wherein the temperature of the double-screw extruder from the feeding section to the machine head is respectively as follows: 220 ℃, 260 ℃, 255 ℃, 250 ℃ and 250 ℃ of a die head.
Example 5
1) Firstly, 60.5 parts of polyamide EPR24, 0.7 part of lubricant ethylene bis stearamide EBS (P-130), 0.4 part of antioxidant 1098 and 0.4 part of antioxidant 168 are mixed, and then 13 parts of halogen-free flame retardant hypophosphite OP1312 and 5 parts of silicon stannate are added and mixed to obtain a mixed material;
2) adding the mixed material from a main feed of a double-screw extruder, adding 20 parts of the alkali-free glass fiber ECS301HP serving as the reinforcing modifier from a measuring feed port of the extruder, and performing melt extrusion, cooling and cutting to obtain the flame-retardant polyamide material; wherein the temperature of the double-screw extruder from the feeding section to the machine head is respectively as follows: 240 ℃, 275 ℃, 280 ℃, 275 ℃, 270 ℃, 265 ℃, 260 ℃ and 270 ℃ and a die temperature of 270 ℃.
In addition, according to the prior art, the halogen-free flame retardant polyamide material uses a halogen-free flame retardant to achieve the flame retardant property of the modified polyamide, and the following comparative examples are prepared:
comparative example 1
1) Firstly, 10 parts of polyamide EPR24, 44 parts of M1013B, 0.5 part of lubricant ethylene bis stearamide EBS (P-130), 0.2 part of antioxidant 1098 and 0.3 part of antioxidant 168 are mixed, and then 15 parts of halogen-free flame retardant hypophosphite OP1312 is added and mixed to obtain a mixed material;
2) adding the mixed material from a main feed of a double-screw extruder, adding 30 parts of the alkali-free glass fiber ECS301HP serving as the reinforcing modifier from a measuring feed port of the extruder, and performing melt extrusion, cooling and cutting to obtain the flame-retardant polyamide material; wherein the temperature of the double-screw extruder from the feeding section to the machine head is respectively as follows: 220 ℃, 260 ℃, 255 ℃, 250 ℃ and 250 ℃ of a die head.
Comparative example 2
1) Firstly, 60.5 parts of polyamide EPR24, 0.7 part of lubricant ethylene bis stearamide EBS (P-130), 0.4 part of antioxidant 1098 and 0.4 part of antioxidant 168 are mixed, and then 18 parts of halogen-free flame retardant hypophosphite OP1312 is added and mixed to obtain a mixed material;
2) adding the mixed material from a main feed of a double-screw extruder, adding 20 parts of the alkali-free glass fiber ECS301HP serving as the reinforcing modifier from a measuring feed port of the extruder, and performing melt extrusion, cooling and cutting to obtain the flame-retardant polyamide material; wherein the temperature of the double-screw extruder from the feeding section to the machine head is respectively as follows: 240 ℃, 275 ℃, 280 ℃, 275 ℃, 270 ℃, 265 ℃, 260 ℃ and 270 ℃ and a die temperature of 270 ℃.
The specific raw material ratios of the above examples 1-5 and comparative examples 1-2 are shown in Table 1:
TABLE 1 raw material proportioning table (parts by weight)
| Prescription table | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 |
| EPR24 | 40 | - | 40 | 10 | 60.5 | 10 | 60.5 |
| M1013B | - | 58 | 32 | 44 | - | 44 | - |
| OP1312 | 15 | 10 | 15 | 8 | 13 | 15 | 18 |
| Stannic acid silicon | 3 | 6.5 | 9 | 7 | 5 | - | - |
| EBS(P-130) | 1 | 0.2 | 0.4 | 0.5 | 0.7 | 0.5 | 0.7 |
| 1098 | 0.5 | 0.1 | 0.3 | 0.2 | 0.4 | 0.2 | 0.4 |
| 168 | 0.5 | 0.2 | 0.3 | 0.3 | 0.4 | 0.3 | 0.4 |
| ECS 301HP | 40 | 25 | - | 30 | 20 | 30 | 20 |
According to the mixture ratio of the examples 1-5 and the comparative examples 1-2 in the table 1, respectively extruding and granulating on a screw extruder by using a conventional method and process for producing polyamide materials, then injection-molding the particles into various sample strips, and testing the sample strips for various mechanical, flame retardant, GWIT and other properties according to corresponding test standards, wherein the performance test standards are as follows:
the tensile strength is tested according to ISO527 standard, and the tensile speed is 5 mm/min;
the bending strength is tested according to ISO178 standard, and the bending speed is 2 mm/min;
the bending modulus is tested according to ISO178 standard, and the bending speed is 2 mm/min;
the impact of the simple beam notch is tested according to ISO179-1 standard;
the flame retardance is tested according to UL94 standard, and the thickness of a sample strip is 1.6mm;
GWIT was tested according to IEC60695-2-13 standard and the specimens were 2mm thick.
The results of the performance tests are shown in table 2:
TABLE 2 Performance testing of products
| Performance of | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 |
| Tensile strength MPa | 170 | 130 | 72 | 139 | 107 | 128 | 105 |
| Bending strength MPa | 255 | 180 | 100 | 210 | 178 | 195 | 175 |
| Flexural modulus MPa | 9210 | 6970 | 2650 | 7800 | 6550 | 7420 | 6480 |
| Impact strength kJ/m of simply supported beam gap2 | 98 | 7.0 | 5.5 | 7.8 | 6.3 | 7.5 | 6.0 |
| Flame retardancy (1.6mm) | V-0 | V-0 | V-0 | V-0 | V-0 | V-1 | V-0 |
| GWIT (2mm)/℃ | 960 | 960 | 960 | 960 | 960 | 750 | 800 |
As can be seen from examples 1 to 5 and comparative examples 1 to 2 in Table 2, the amount of hypophosphite OP1312 added is reduced after the addition of the silicon stannate, and the flame retardant property and the mechanical property are more excellent and lower in cost than those of the flame retardant material without the addition of the silicon stannate; the GWIT of the flame-retardant material without the added silicon stannate is still not 960 ℃ although the content of the flame retardant OP1312 is high, and the GWIT of the material after the added silicon stannate can basically reach 960 ℃, so that the GWIT of the material is greatly improved.
It is to be noted that the polyamide of the invention is not limited to PA66 and/or PA6, and the polyamide of the invention may be one of the following polyamides or a mixture of any of them: polycaprolactam (nylon 6), polytetramethyleneadipamide (nylon 46), polyhexamethyleneadipamide (nylon 66), polyhexamethylenesebacamide (nylon 610), polyhexamethylenedodecamide (nylon 612), henamethylenediamide (nylon 116), polyundecanolactam (nylon 11), polydodecanolactam (nylon 12), polyparaphenylene terephthalamide, polyisophthaloyl isophthalamide, polytrimethylhexamethylenediamine terephthalamide, polyhexamethyleneisophthalamide (nylon 6I), polytrimethylmethylenediamine nonapthalate (nylon 9T), polyhexamethyleneterephthalamide (nylon 6T), nylon 10T, nylon 12T, nylon 10T/1012, nylon 6/6T, nylon 46/10T, and polydodecanedioic bis (4-aminocyclohexyl) methane (nylon PACM 12).
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the technical principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (6)
1. The halogen-free flame-retardant polyamide material is characterized by comprising the following main components in parts by weight:
40-72 parts of polyamide, namely,
8-15 parts of a halogen-free flame retardant,
3-9 parts of a flame-retardant synergist,
0.5-2 parts of a processing aid,
0-40 parts of a reinforcing modifier;
wherein,
the halogen-free flame retardant is hypophosphite;
the flame-retardant synergist is silicon stannate with silicon content of 30-60%.
2. The halogen-free flame-retardant polyamide material as claimed in claim 1, wherein the polyamide is one or a mixture of any of the following polyamides: nylon 6, polytetramethyleneadipamide, nylon 66, polyhexamethylenesebacamide, polyhexamethylenedodecanediamine, undecamethyleneadipamide, polyundecanolactam, polydodecanolactam, polyparaphenylene terephthalamide, polyisophthaloyl-m-phenylenediamine, polyparaphenylene trimethylhexamethylenediamine, polyisophthaloyl-hexamethylenediamine, polyparaphenylene nonamethylenediamine, polyparaphenylene terephthalamide, nylon 10T, nylon 12T, nylon 10T/1012, nylon 6/6T, nylon 46/10T, polydodecane-bis (4-aminocyclohexyl) methane.
3. The halogen-free flame-retardant polyamide material as claimed in claim 1 or 2, characterized in that the processing aids are lubricants and antioxidants.
4. Halogen free flame retardant polyamide material according to claim 3, characterized in that the reinforcing modifier is alkali free glass fiber.
5. Halogen free flame retardant polyamide material according to claim 4, characterized in that the polyamide is nylon 6 and/or nylon 66.
6. The process for the preparation of halogen free flame retardant polyamide material according to any of claims 1 to 5, characterized in that it comprises the following steps:
1) preparing materials according to the parts by weight;
2) firstly, mixing polyamide and a processing aid, and then adding a halogen-free flame retardant and a flame-retardant synergist for mixing to obtain a mixed material;
3) adding the mixed material from a main feeding port of a double-screw extruder, adding the reinforcing modifier from a side feeding port of the extruder, and performing melt extrusion, cooling and grain cutting to obtain the halogen-free flame-retardant polyamide material; wherein the temperatures of the twin-screw extruder from the feeding section to the head are respectively as follows: 210-240 ℃, 230-275 ℃, 245-280 ℃, 245-275 ℃, 240-270 ℃, 235-265 ℃, 230-260 ℃ and 235-270 ℃ of the die head.
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