CN113278222A - Ultrahigh-flow halogen-free flame-retardant PP material and preparation method thereof - Google Patents
Ultrahigh-flow halogen-free flame-retardant PP material and preparation method thereof Download PDFInfo
- Publication number
- CN113278222A CN113278222A CN202110643814.7A CN202110643814A CN113278222A CN 113278222 A CN113278222 A CN 113278222A CN 202110643814 A CN202110643814 A CN 202110643814A CN 113278222 A CN113278222 A CN 113278222A
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- Prior art keywords
- halogen
- free flame
- retardant
- peroxide
- raw materials
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- 239000003063 flame retardant Substances 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 28
- 239000000463 material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000004743 Polypropylene Substances 0.000 claims abstract description 41
- 229920001155 polypropylene Polymers 0.000 claims abstract description 32
- 150000002978 peroxides Chemical class 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 14
- -1 polypropylene Polymers 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000155 melt Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001125 extrusion Methods 0.000 claims abstract description 3
- 238000005469 granulation Methods 0.000 claims abstract description 3
- 230000003179 granulation Effects 0.000 claims abstract description 3
- 238000005303 weighing Methods 0.000 claims abstract description 3
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 4
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- KWAYGHBLGWNQBS-UHFFFAOYSA-N silicon;triazine Chemical compound [Si].C1=CN=NN=C1 KWAYGHBLGWNQBS-UHFFFAOYSA-N 0.000 claims description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 239000004605 External Lubricant Substances 0.000 description 1
- 239000004610 Internal Lubricant Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- 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
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- 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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Abstract
The invention relates to an ultrahigh-flow halogen-free flame-retardant PP material and a preparation method thereof. The composite material is characterized by being prepared from the following raw materials in percentage by weight: 70-80% of polypropylene, 20-30% of halogen-free flame retardant, 0.1-0.5% of peroxide, 0.01-0.1% of anti-dripping agent and 0.1-1% of antioxidant. The preparation method comprises the following steps: weighing the raw materials according to the weight percentage; putting all raw materials except peroxide into a high-speed mixer to be mixed for 5-15 minutes; dissolving peroxide with alcohol or acetone, and adding into the fifth section of the extruder; the mixed raw materials are put into a double-screw extruder for extrusion granulation, the rotating speed of the screw is 200-500 r/min, and the temperature is 170-230 ℃. The invention can adjust and control the melt index of the flame-retardant PP by quantitatively adding the peroxide, is well matched with battery shells with various specifications and sizes for use, and has wide market prospect.
Description
Technical Field
The invention relates to an ultrahigh-flow halogen-free flame-retardant PP material and a preparation method thereof, which can be widely applied to the production of large-sized thin-wall plastic products, particularly the field of new energy battery manufacture, and belongs to the technical field of high polymer materials.
Background
Polypropylene (PP) is one of five general-purpose plastics, has excellent comprehensive performance and low price, and is widely applied. Aiming at the defects of low strength, low heat resistance and extremely easy combustion of PP materials, people perform various modifications, reinforcement, toughening, flame retardance and the like on the PP materials, so that the application range of the modified PP is greatly expanded. The flame-retardant PP material is mainly used for shells of household appliances and electronic appliances. In recent years, with the rapid development of new energy automobiles, flame-retardant PP materials are used for producing battery lining shells. However, the flowability of PP is greatly reduced after a large amount of flame retardant is added, so that some thin-walled products are difficult to produce.
Chinese patent document CN 101805480 a discloses a flame retardant polypropylene material and a preparation method thereof, wherein the flame retardant polypropylene material is prepared from the following raw materials in percentage by weight: 75.5-83.7% of polypropylene, 6-10% of thermoplastic elastomer, 3-7% of compatilizer, 0.2% of white oil, 4-6% of flame retardant, 0.6-1% of lubricant and 0.3% of antioxidant; the obtained flame-retardant polypropylene material has the characteristics of high fluidity, high impact resistance, low density and high gloss, can be used in the fields of household appliances such as air conditioners, washing machines, refrigerators, televisions and the like, and has a maximum melt index of only 9.3g/10 min. Chinese patent N102040775A discloses a flame retardant PP material, which comprises the following components in parts by mass: 25-50% of high-fluidity homo-polypropylene, 25-50% of high-fluidity co-polypropylene, 10-33% of flame retardant, 5-30% of inorganic reinforcing agent, 1-10% of barrier additive, 0.1-3% of heat-resistant reinforcing agent, 0.1-4% of antioxidant and nucleating agent, 0.1-3% of composite pigment and 1-5% of internal and external lubricant; but the melt index is only 4.3g/10min at the maximum. Chinese patent N103694561A discloses a high-flow high-gloss flame-retardant toughened polypropylene material and a preparation method thereof. The material comprises the following components in parts by weight: 100 parts of polypropylene; 5-10 parts of a toughening agent; 1-5 of graft; 10-20 parts of high-gloss barium sulfate; 10-14 parts of flame retardant; 5-7 parts of auxiliary flame retardant; 0.05 to 0.2 of nucleating agent; 0.2 to 0.4 percent of antioxidant; 0.2-0.4 of surface treating agent; 0.2-0.5 of dispersing lubricant; 0.03 parts of fluorescent whitening agent; the melt index of the alloy reaches 25g/10min at the maximum. Other patents are not disclosed herein.
Disclosure of Invention
The invention aims to provide an ultrahigh-flow halogen-free flame-retardant PP material and a preparation method thereof, which can enable the fluidity of flame-retardant PP to reach more than 100 at most and the fluidity of normally produced flame-retardant PP to reach more than 60 by adding peroxide, and can meet the production requirements of new energy batteries with various sizes.
The invention relates to an ultrahigh-flow halogen-free flame-retardant PP material which mainly comprises the following raw materials in percentage by weight:
wherein the polypropylene is homopolymerized polypropylene, and the melt index is between 10 and 40g/10min under the conditions of 190 ℃ and 2.16Kg weight.
The halogen-free flame retardant is a combination of ammonium polyphosphate and a silicon triazine charring agent, and the combination ratio of the ammonium polyphosphate to the silicon triazine charring agent is 20: 1.
The peroxide is one of dicumyl peroxide or di-tert-butyl peroxide.
The anti-dripping agent is polytetrafluoroethylene powder, the molecular weight of the anti-dripping agent is 10000-20000, and the particle size of the anti-dripping agent is 5-15 mu m.
The antioxidant is a hindered phenol antioxidant or a phosphite antioxidant compound, the hindered phenol antioxidant is 1010, and the phosphite antioxidant compound is 1010 and 168.
The ultrahigh-flow halogen-free flame-retardant PP material is characterized by comprising the following steps of:
1. weighing the raw materials according to the weight percentage;
2. putting all raw materials except peroxide into a high-speed mixer to be mixed for 5-15 minutes;
3. dissolving peroxide with alcohol or acetone, and adding into the fifth section of the extruder;
4. the mixed raw materials are put into a double-screw extruder for extrusion granulation, the rotating speed of the screw is 200-500 r/min, and the temperature is 170-230 ℃.
Compared with the prior art, the flame-retardant PP battery case disclosed by the invention can adjust and control the melt index of the flame-retardant PP through the quantitative addition of the peroxide, and is well matched with battery cases with various specifications and sizes for use.
Detailed description of the preferred embodiments
The present invention is described in further detail with reference to the following examples, but the embodiments of the present invention are not limited thereto, and the described examples are only a part of examples of the present invention, but not all examples. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
An ultrahigh-flow halogen-free flame-retardant PP material and a preparation method thereof, which comprises the following steps:
the raw materials of all the components except peroxide are added into a high-speed mixer according to the weight percentage for even stirring and dispersion, the mixture is discharged and is placed into a double-screw extruder for melting, blending, extruding and granulating, the peroxide is dissolved by alcohol or acetone, and the mixture is added into the fifth section of the extruder in a metering way. The process conditions of the extruder are as follows: the temperature of the twin-screw extruder in the 1-2 area is 170-180 ℃, the temperature of the twin-screw extruder in the 3-4 area is 180-190 ℃, the temperature of the twin-screw extruder in the 5-6 area is 190-230 ℃, the temperature of the twin-screw extruder in the 7-8 area is 190-210 ℃, the temperature of the extruder head is 180-200 ℃, and the rotating speed of the screws is 200-500 revolutions per minute.
Table 1 shows examples and comparative examples prepared in different proportions by weight.
Examples 1, 2, 3 and comparative example (Table 1)
| Components | Example 1 | Example 2 | Example 3 | Comparative example |
| Polypropylene (Y2600) | 69.69 | 74.35 | 78.90 | 74.55 |
| Halogen-free flame retardant | 30 | 25 | 20 | 25 |
| Peroxides and their use in the preparation of pharmaceutical preparations | 0.1 | 0.2 | 0.5 | 0 |
| Anti-dripping agent | 0.01 | 0.05 | 0.1 | 0.05 |
| 1010/168(1:1) | 0.2 | 0.4 | 0.5 | 0.4 |
Drying the ultrahigh-flow halogen-free flame-retardant PP material finished by the method at 80 ℃ for 6 hours, and then performing injection molding on the material to form an ISO standard sample strip, wherein the tensile strength is tested according to ISO527-2 standard; the flexural strength and flexural modulus were tested according to ISO178 standard; the notched impact strength is tested according to ISO179-1/1eA standard; the flame retardance is tested according to UL-94 standard; the melt index was measured according to ISO1133(190 ℃, 2.16 KG). The results are shown in Table 2.
Mechanical Properties of examples 1, 2, 3 and comparative example (Table 2)
As can be seen from the performances of the example 2 and the comparative example, on the premise that the performances are almost consistent, the fluidity of the invention is more than three times that of the comparative example, and the fluidity can be increased to more than 100g/10min from 35g/10min, so that the invention has wide applicability and wide market prospect.
Claims (7)
1. The ultrahigh-flow halogen-free flame-retardant PP material is characterized by being mainly prepared from the following raw materials in percentage by weight:
2. the halogen-free flame retardant PP material with ultra-high flow as claimed in claim 1, wherein the polypropylene is homo polypropylene and has a melt index of 10-40g/10min at 190 ℃ under a weight of 2.16 Kg.
3. The ultra-high flow halogen-free flame retardant PP material of claim 1, wherein the halogen-free flame retardant is a combination of ammonium polyphosphate and a silicon triazine char forming agent, and the combination ratio of the ammonium polyphosphate to the silicon triazine char forming agent is 20: 1.
4. The ultra-high flow halogen-free flame retardant PP material of claim 1 wherein said peroxide is one of dicumyl peroxide or di-t-butyl peroxide.
5. The ultra-high flow halogen-free flame retardant PP material as claimed in claim 1, wherein the anti-dripping agent is polytetrafluoroethylene powder with a molecular weight of 10000-.
6. The ultrahigh-flow halogen-free flame-retardant PP material according to claim 1 is characterized in that the antioxidant is a hindered phenol antioxidant or a phosphite antioxidant compound, the hindered phenol antioxidant is 1010, and the phosphite antioxidant compound is 1010 and 168.
7. The method for preparing the halogen-free flame retardant PP material with ultra-high flow as claimed in any one of claims 1 to 6, wherein the method comprises the following steps:
1. weighing the raw materials according to the weight percentage;
2. putting all raw materials except peroxide into a high-speed mixer to be mixed for 5-15 minutes;
3. dissolving peroxide with alcohol or acetone, and adding into the fifth section of the extruder;
4. the mixed raw materials are put into a double-screw extruder for extrusion granulation, the rotating speed of the screw is 200-500 r/min, and the temperature is 170-230 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110643814.7A CN113278222A (en) | 2021-06-09 | 2021-06-09 | Ultrahigh-flow halogen-free flame-retardant PP material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110643814.7A CN113278222A (en) | 2021-06-09 | 2021-06-09 | Ultrahigh-flow halogen-free flame-retardant PP material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113278222A true CN113278222A (en) | 2021-08-20 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110643814.7A Pending CN113278222A (en) | 2021-06-09 | 2021-06-09 | Ultrahigh-flow halogen-free flame-retardant PP material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113278222A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995123A (en) * | 2006-12-28 | 2007-07-11 | 深圳市科聚新材料有限公司 | Polypropylene material and its preparing process |
| CN110894319A (en) * | 2019-10-28 | 2020-03-20 | 中广核俊尔（上海）新材料有限公司 | Polypropylene material for battery cover plate and preparation method thereof |
-
2021
- 2021-06-09 CN CN202110643814.7A patent/CN113278222A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995123A (en) * | 2006-12-28 | 2007-07-11 | 深圳市科聚新材料有限公司 | Polypropylene material and its preparing process |
| CN110894319A (en) * | 2019-10-28 | 2020-03-20 | 中广核俊尔（上海）新材料有限公司 | Polypropylene material for battery cover plate and preparation method thereof |
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Application publication date: 20210820 |