CN111087688A - Anti-blushing flame-retardant polypropylene ribbon and preparation method thereof - Google Patents
Anti-blushing flame-retardant polypropylene ribbon and preparation method thereof Download PDFInfo
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- CN111087688A CN111087688A CN201911306475.2A CN201911306475A CN111087688A CN 111087688 A CN111087688 A CN 111087688A CN 201911306475 A CN201911306475 A CN 201911306475A CN 111087688 A CN111087688 A CN 111087688A
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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
- 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
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to an anti-blushing flame-retardant polypropylene ribbon and a preparation method thereof. The material comprises the following components in parts by weight: 60-80 parts of polypropylene, 7-30 parts of second component polymer, 10-20 parts of flame retardant toughening agent, 0.5-3 parts of anti-blushing agent and 1-3 parts of other auxiliary agents. The invention creatively prepares the flame-retardant toughening agent through reactive co-extrusion, and compounds the flame-retardant toughening agent with the stress whitening resistance agent, thereby meeting the flame-retardant requirements of the cable tie, meeting the special requirements of the cable tie on mechanics, low-temperature toughness, humidity resistance, heat resistance, whitening resistance and the like, and having no precipitation of the flame retardant. The flame retardant toughening agent greatly solves the problem that the traditional flame retardant is difficult to disperse in polypropylene, and effectively improves the uniformity of the material. Meanwhile, the product has the characteristics of high production efficiency and easy demoulding, and meets the production requirement of 64-degree or even higher production of the product in one mould.
Description
Technical Field
The invention relates to an anti-blushing flame-retardant polypropylene ribbon and a preparation method thereof, belonging to the technical field of materials.
Background
The polypropylene strapping tape has been widely used in various fields because of its advantages of good plasticity, good breaking tension, bending resistance, light specific gravity, convenient use, etc. In the use process, especially when the internal structure of a household appliance is used, the polypropylene ribbon is required to have a flame retardant function and low smoke emission, and the flame retardant generally can only select halogen-free flame retardant, but the halogen-free flame retardant in the current market faces a plurality of problems when used for the polypropylene ribbon, such as: 1. 2, in the using process of the existing halogen-free flame retardant, especially in a damp and hot environment, the surface migration resistance of the material is poor, the material is easy to separate out, the flame retardant effect is poor, and the product performance is damaged.
Disclosure of Invention
In order to solve the technical problems, the flame-retardant toughening agent is creatively prepared by reactive co-extrusion and compounded with the stress whitening resistance agent, so that the flame-retardant requirement of the cable tie is met, the special requirements of the cable tie on mechanics, low-temperature toughness, humidity and heat resistance, whitening resistance and the like are met, and the flame retardant is not separated out. The flame retardant toughening agent greatly solves the problem that the traditional flame retardant is difficult to disperse in polypropylene, and effectively improves the uniformity of the material. Meanwhile, the product has the characteristics of high production efficiency and easy demoulding.
In order to achieve the purpose, the invention adopts the following technical scheme:
the whitening-resistant flame-retardant polypropylene cable tie comprises the following components in parts by weight:
60-80 parts of polypropylene
7-30 parts of second component polymer
10-20 parts of flame-retardant toughening agent
0.5-3 parts of anti-blushing agent
1-3 parts of other auxiliary agents
The flame-retardant toughening agent is prepared by the following steps: firstly, blending phosphorus-containing monomers and an initiator in a high-speed mixer, and then dissolving the mixture in acetone; adding the mixed solution into a medium mixer containing a toughening agent and having a temperature of 40-120 ℃, then fully mixing until acetone is volatilized, respectively recovering acetone and solid mixed materials, adding the mixed materials into an extruder with a temperature of 100-200 ℃, and carrying out extrusion granulation to obtain the phosphorus-containing monomer grafted toughening agent. Wherein the rotation speed is 200-800 r/min. Wherein the initiator is one of cumyl peroxide, potassium persulfate, sodium bisulfite, N-dimethylaniline and cerium sulfate, and sodium bisulfite is preferred.
In a further scheme, the polypropylene is bimodal polypropylene, the melting temperature of the bimodal polypropylene is 155-161 ℃, the melt flow rate of the bimodal polypropylene is 0.5-10g/10min, and preferably the bimodal polypropylene has the melting temperature of 158 ℃ and the melt flow rate of 5g/10 min.
In a further embodiment, the second component polymer is bimodal polyethylene with a melt flow rate of 1-25g/10min, preferably 10g/10 min.
In a further embodiment, the whitening resistant agent is a silicone copolymer containing functional groups, such as one of urea groups, urethane groups, amino groups, isocyanate groups, crown ether groups and epoxy groups, and is preferably a crown ether silicone copolymer.
In a further scheme, the flame-retardant toughening agent is one of phosphorus-containing monomer graft modified polyolefin, phosphorus-containing monomer graft modified ethylene- α olefin copolymer, phosphorus-containing monomer graft modified ethylene-propylene rubber and phosphorus-containing monomer graft modified SEBS, preferably phosphorus-containing monomer graft modified ethylene-propylene rubber, wherein the phosphorus-containing monomer is one of aminomethyl phosphonate, hydroxymethyl phosphine oxide, oxyphosphorus heterocyclic hexane phosphonate, triphenyl thiophosphate and diphenyl thiophosphate, and preferably oxyphosphorus heterocyclic hexane phosphonate.
In a further scheme, the other auxiliary agents are an antioxidant, a lubricant, a light stabilizer and black master batch, wherein the antioxidant is one of 1010, 168, 624, 326 and 224, and is preferably the antioxidant 1010; the lubricant is one of calcium stearate, EBS, polyethylene wax and erucamide, preferably erucamide; the light stabilizer is cyanogen 3808; the black master batch is carbon black master batch.
A preparation method of an anti-blushing flame-retardant polypropylene ribbon comprises the following steps:
(1) firstly, 5 to 25 parts of phosphorus-containing monomer and 0.1 to 0.5 part of initiator are blended in a high-speed mixer and then dissolved in acetone; adding the mixed solution into a medium mixer containing 70-90 parts of toughening agent and at the temperature of 40-120 ℃, then fully mixing until acetone is volatilized, respectively recovering acetone and solid mixed materials, adding the mixed materials into an extruder at the temperature of 100-200 ℃, and carrying out extrusion granulation to obtain the phosphorus-containing monomer grafted toughening agent, namely the flame-retardant toughening agent; wherein, the rotating speed of the high-speed mixer is 200-. Wherein the initiator is one of cumyl peroxide, potassium persulfate, sodium bisulfite, N-dimethylaniline and cerium sulfate, and sodium bisulfite is preferred.
(2) 60-80 parts of polypropylene, 7-30 parts of second component polymer, 10-20 parts of flame retardant toughening agent, 0.5-3 parts of anti-whitening agent and 1-3 parts of other auxiliary agents are put into a high-speed mixer for mixing, the mixture is added into a double-screw extruder through a hopper, and the anti-whitening flame retardant polypropylene ribbon material is obtained through meshing plasticization, mixing, extrusion, bracing, air drying and granulation; wherein, the extruder temperature sets up a district to the aircraft nose: 160 ℃ and 220 ℃.
Advantageous effects
1. According to the invention, the flame-retardant toughening agent with the flame-retardant element and the whitening resistant agent are compounded, so that the balance of good mechanical strength and toughness of the flame-retardant polypropylene ribbon is realized, the flame-retardant UL941.6 mm reaches the V1 level, the flame-retardant requirement of the ribbon is met, the problems of surface mobility and stress whitening of the ribbon of the flame-retardant polypropylene ribbon product are effectively solved, and the flame-retardant level can not be reduced through the boiling experiment of the ribbon. The invention creatively adopts the flame-retardant toughening agent to effectively improve the dispersion of the flame retardant in the nonpolar polypropylene material and the binding force with the matrix, thereby improving the mechanical properties of the flame-retardant polypropylene ribbon, in particular the toughness and the impact strength of the material. Meanwhile, the product has the characteristics of environmental protection, high dimensional stability and the like, and meets the key material requirements of products such as household appliances, new energy automobiles and the like.
2. According to the invention, polypropylene and polyethylene with a bimodal distribution structure are selected for compounding, so that the forming performance of the material can be effectively improved, and the requirements of multiple mold cavities, complex structure and thin-wall ribbon processing forming performance can be met; in addition, the short-period rapid injection molding can be realized, and the production efficiency is improved.
3. The preparation method of the material has the advantages of economic process, easy operation, high production efficiency and easy realization of industrialization.
4. The invention creatively prepares the flame-retardant toughening agent through reactive co-extrusion, and compounds the flame-retardant toughening agent with the stress whitening resistance agent, thereby meeting the flame-retardant requirements of the cable tie, meeting the special requirements of the cable tie on mechanics, low-temperature toughness, humidity resistance, heat resistance, whitening resistance and the like, and having no precipitation of the flame retardant. The flame retardant toughening agent greatly solves the problem that the traditional flame retardant is difficult to disperse in polypropylene, and effectively improves the uniformity of the material. Meanwhile, the product has the characteristics of high production efficiency and easy demoulding, and meets the production requirement of 64-degree or even higher production of the product in one mould.
Drawings
Fig. 1 is an SEM image of the poaching resistance precipitation test of comparative example 1.
FIG. 2 is an SEM image of the boiling resistance test of the example.
Detailed Description
The present invention will be described in further detail with reference to examples. Examples
A preparation method of an anti-blushing flame-retardant polypropylene ribbon comprises the following steps:
(1) firstly, 5 to 25 parts of phosphorus-containing monomer and 0.1 to 0.5 part of initiator are blended in a high-speed mixer and then dissolved in acetone; adding the mixed solution into a medium mixer containing 70-90 parts of toughening agent and at the temperature of 40-120 ℃, then fully mixing until acetone is volatilized, respectively recovering acetone and solid mixed materials, adding the mixed materials into an extruder at the temperature of 100-200 ℃, and carrying out extrusion granulation to obtain the phosphorus-containing monomer grafted toughening agent, namely the flame-retardant toughening agent; wherein, the rotation speed of the high-speed mixer is 200-. Wherein the initiator is one of cumyl peroxide, potassium persulfate, sodium bisulfite, N-dimethylaniline and cerium sulfate, and sodium bisulfite is preferred.
(2) 60-80 parts of polypropylene, 7-30 parts of second component polymer, 10-20 parts of flame retardant toughening agent, 0.5-3 parts of anti-whitening agent and 1-3 parts of other auxiliary agents are put into a high-speed mixer for mixing, the mixture is added into a double-screw extruder through a hopper, and the anti-whitening flame retardant polypropylene ribbon material is obtained through meshing plasticization, mixing, extrusion, bracing, air drying and granulation; wherein, the extruder temperature sets up a district to the aircraft nose: 160 ℃ and 220 ℃.
The polypropylene is bimodal polypropylene, the melting temperature of the bimodal polypropylene is 155-161 ℃, the melt flow rate of the bimodal polypropylene is 0.5-10g/10min, and the preferred bimodal polypropylene has the melting temperature of 158 ℃ and the melt flow rate of 5g/10 min.
The second component polymer is bimodal polyethylene with a melt flow rate of 1-25g/10min, preferably 10g/10 min.
The anti-whitening agent is a silicone copolymer containing functional groups, such as one of urea groups, urethane groups, amino groups, isocyanate groups, crown ether groups and epoxy groups, and the crown ether-based silicone copolymer is preferred.
The flame-retardant toughening agent is one of phosphorus-containing monomer graft modified polyolefin, phosphorus-containing monomer graft modified ethylene- α olefin copolymer, phosphorus-containing monomer graft modified ethylene-propylene rubber and phosphorus-containing monomer graft modified SEBS, preferably phosphorus-containing monomer graft modified ethylene-propylene rubber, wherein the phosphorus-containing monomer is one of aminomethyl phosphonate, hydroxymethyl phosphine oxide, oxyphosphate, triphenyl thiophosphate and diphenyl thiophosphate, and preferably oxyphosphate.
The other auxiliary agents are an antioxidant, a lubricant, a light stabilizer and black master batch, wherein the antioxidant is one of 1010, 168, 624, 326 and 224, and is preferably the antioxidant 1010; the lubricant is one of calcium stearate, EBS, polyethylene wax and erucamide, preferably erucamide; the light stabilizer is cyanogen 3808; the black master batch is carbon black master batch.
3 anti-blushing flame-retardant polypropylene ribbon materials and comparative examples are prepared by adjusting the specific components and parts according to the method, and the specific formula is shown in the following table 1.
Table 1 comparative and 3 example formulations
| Components | Comparative example 1 | Example 1 | Example 2 | Example 3 |
| Polypropylene | 80 | 60 | 80 | 70 |
| Polyethylene | 30 | 7 | 20 | |
| Amino silicone copolymers | 3 | |||
| Crown ether based silicone copolymerizationArticle (A) | 0.5 | |||
| Epoxy-based silicone copolymers | 2 | |||
| Commercial flame retardant HZ-2030M | 20 | |||
| Oxaphosphorocyclohexane phosphonate grafted polyethylene | 20 | |||
| Triphenylthiophosphate grafted ethylene- α olefin copolymer | 10 | |||
| Diphenyl thiophosphate grafted ethylene-propylene rubber | 15 | |||
| Antioxidant 1010 | 0.5 | 0.5 | ||
| Antioxidant 168 | 0.2 | 0.6 | ||
| EBS | 0.5 | 0.2 | ||
| Erucamide | 0.3 | 0.6 | ||
| Cyanite 3808 | 0.2 | 0.1 | 0.3 | |
| Black masterbatch | 1 | 1 | 0.5 | 1.5 |
The performance results of the above comparative and examples are shown in the following table:
table 2 table of properties of examples of products according to the invention
| Detecting items | Standard of merit | Comparative example 1 | Example 2 | Example 3 | Example 4 |
| Tensile strength/MPa | ISO 527 | 18 | 21 | 23 | 22 |
| Flexural modulus/MPa | ISO 178 | 1210 | 1490 | 1780 | 1600 |
| Notched Izod impact Strength/kJ/m2（23℃） | ISO 179 | 3.1 | 25.6 | 16.4 | 18.6 |
| Notched Izod impact Strength/kJ/m2（-30℃） | ISO 179 | 2.0 | 5.7 | 4.5 | 5.0 |
| Flame retardant rating | UL 94/1.6mm | V-1 | V-1 | V-1 | V-1 |
Through the tables, the material provided by the invention has the advantages that the requirements of the flame retardant grade of the cable tie are met, meanwhile, the material provided by the invention has higher strength, modulus and impact toughness, the performances are all derived from good compatibility among the components of the material, and the characteristics enable the material provided by the invention to meet the use requirements of the flame retardant cable tie on precipitation resistance, whitening resistance and the like.
By the comparative example and the inventive example boiling resistant precipitation test: the product is placed at 100 ℃, boiled in water for 7 days, the precipitation condition of the surface flame retardant powder is observed, the boiled product is subjected to a scanning electron microscope, and the test result is shown in figures 1 and 2. As can be seen from the figure, the precipitation amount of the inventive example after being boiled with water is obviously lower than that of the comparative example, which shows that the precipitation resistance of the inventive material is obviously better than that of the comparative example.
The above description is only for the specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and any equivalent changes or modifications made by those skilled in the art according to the spirit of the present invention should be covered within the scope of the present invention.
Claims (11)
1. The whitening-resistant flame-retardant polypropylene ribbon is characterized by comprising the following components in parts by weight:
60-80 Parts of Polypropylene (PP),
7-30 parts of a second component polymer,
10-20 parts of a flame-retardant toughening agent,
0.5 to 3 portions of anti-blushing agent,
1-3 parts of other auxiliary agents.
2. The whitening-resistant flame-retardant polypropylene ribbon as defined in claim 1, wherein:
the flame retardant toughening agent is prepared by the following method: firstly, 5 to 25 parts of phosphorus-containing monomer and 0.1 to 0.5 part of initiator are blended in a high-speed mixer and then dissolved in acetone; adding the mixed solution into a medium mixer containing 70-90 parts of toughening agent and at the temperature of 40-120 ℃, then fully mixing until acetone is volatilized, respectively recovering acetone and solid mixed materials, adding the mixed materials into an extruder at the temperature of 100-200 ℃, and carrying out extrusion granulation to obtain the phosphorus-containing monomer grafted toughening agent, namely the flame-retardant toughening agent; wherein, the rotating speed of the high-speed mixer is 200-.
3. The blush-resistant flame-retardant polypropylene ribbon according to claim 1 or 2, wherein:
the flame-retardant toughening agent is one of phosphorus-containing monomer graft modified polyolefin, phosphorus-containing monomer graft modified ethylene- α olefin copolymer, phosphorus-containing monomer graft modified ethylene propylene rubber and phosphorus-containing monomer graft modified SEBS, wherein the phosphorus-containing monomer is one of aminomethylphosphonate, hydroxymethylphosphine oxide, oxyphosphatehexane phosphonate, triphenyl thiophosphate and diphenyl thiophosphate.
4. The whitening-resistant flame-retardant polypropylene ribbon as defined in claim 3, wherein: the flame-retardant toughening agent is phosphorus-containing monomer graft modified ethylene propylene rubber; the phosphorus-containing monomer is oxyphosphate ester.
5. The whitening-resistant flame-retardant polypropylene ribbon as defined in claim 2, wherein: the initiator is one of cumyl peroxide, potassium persulfate, sodium bisulfite, N-dimethylaniline and cerium sulfate.
6. The whitening-resistant flame-retardant polypropylene ribbon as defined in claim 2, wherein: the initiator is sodium bisulfite.
7. The whitening-resistant flame-retardant polypropylene ribbon as defined in claim 1, wherein: the polypropylene is
The bimodal polypropylene has the melting temperature of 155-;
the second component polymer is bimodal polyethylene with a melt flow rate of 1-25g/10 min.
8. The whitening-resistant flame-retardant polypropylene ribbon as defined in claim 7, wherein:
the polypropylene is bimodal polypropylene with a melting temperature of 158 ℃ and a melt flow rate of 5g/10 min. The second component polymer is a bimodal polyethylene having a melt flow rate of 10g/10 min.
9. The whitening-resistant flame-retardant polypropylene ribbon as defined in claim 1, wherein: the anti-whitening agent is an organic silicon copolymer containing functional groups, and the functional groups are one of carbamido, urethane, amino, isocyanate, crown ether and epoxy;
the other auxiliary agents are an antioxidant, a lubricant, a light stabilizer and black master batch; wherein the antioxidant is one of 1010, 168, 624, 326 and 224; the lubricant is one of calcium stearate, EBS, polyethylene wax and erucamide; the light stabilizer is cyanogen 3808; the black master batch is carbon black master batch.
10. The whitening-resistant flame-retardant polypropylene ribbon as defined in claim 9, wherein: the anti-blushing agent is a crown ether-based organic silicon copolymer;
the antioxidant is antioxidant 1010
The lubricant is erucamide.
11. A method for preparing a whitening-resistant flame-retardant polypropylene ribbon as claimed in any one of claims 1 to 10, wherein: the method comprises the following steps:
(1) firstly, 5 to 25 parts of phosphorus-containing monomer and 0.1 to 0.5 part of initiator are blended in a high-speed mixer and then dissolved in acetone; adding the mixed solution into a medium mixer containing 70-90 parts of toughening agent and at the temperature of 40-120 ℃, then fully mixing until acetone is volatilized, respectively recovering acetone and solid mixed materials, adding the mixed materials into an extruder at the temperature of 100-200 ℃, and carrying out extrusion granulation to obtain the phosphorus-containing monomer grafted toughening agent, namely the flame-retardant toughening agent; wherein the rotating speed of the high-speed mixer is 200-800r/min, and the initiator is one of cumene peroxide, potassium persulfate, sodium bisulfite, N-dimethylaniline and cerium sulfate.
(2) 60-80 parts of polypropylene, 7-30 parts of second component polymer, 10-20 parts of flame retardant toughening agent, 0.5-3 parts of anti-whitening agent and 1-3 parts of other auxiliary agents are put into a high-speed mixer for mixing, the mixture is added into a double-screw extruder through a hopper, and the anti-whitening flame retardant polypropylene ribbon material is obtained through meshing plasticization, mixing, extrusion, bracing, air drying and granulation; wherein, the extruder temperature sets up a district to the aircraft nose: 160 ℃ and 220 ℃.
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Cited By (1)
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