CN114672131B - Automatic micro-crosslinking halogen-free flame-retardant thermoplastic elastomer and preparation method thereof - Google Patents
Automatic micro-crosslinking halogen-free flame-retardant thermoplastic elastomer and preparation method thereof Download PDFInfo
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- CN114672131B CN114672131B CN202210529964.XA CN202210529964A CN114672131B CN 114672131 B CN114672131 B CN 114672131B CN 202210529964 A CN202210529964 A CN 202210529964A CN 114672131 B CN114672131 B CN 114672131B
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- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 75
- 238000004132 cross linking Methods 0.000 title claims abstract description 57
- 239000003063 flame retardant Substances 0.000 title claims abstract description 40
- 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 32
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000000945 filler Substances 0.000 claims abstract description 91
- 239000012796 inorganic flame retardant Substances 0.000 claims abstract description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 67
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910000077 silane Inorganic materials 0.000 claims abstract description 63
- 229920001112 grafted polyolefin Polymers 0.000 claims abstract description 44
- 229920000098 polyolefin Polymers 0.000 claims abstract description 36
- 239000011347 resin Substances 0.000 claims abstract description 36
- 229920005989 resin Polymers 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 35
- 239000008041 oiling agent Substances 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 5
- 230000007062 hydrolysis Effects 0.000 claims abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 5
- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- 150000004668 long chain fatty acids Chemical class 0.000 claims abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 150000002500 ions Chemical group 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 34
- 239000002245 particle Substances 0.000 claims description 31
- 239000004743 Polypropylene Substances 0.000 claims description 28
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 26
- 239000011258 core-shell material Substances 0.000 claims description 25
- 239000004698 Polyethylene Substances 0.000 claims description 23
- -1 polyethylene Polymers 0.000 claims description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 16
- 239000000347 magnesium hydroxide Substances 0.000 claims description 16
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 230000003014 reinforcing effect Effects 0.000 claims description 14
- 239000001993 wax Substances 0.000 claims description 14
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 11
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 claims description 11
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 11
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 10
- 238000013329 compounding Methods 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 10
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 9
- 229920001903 high density polyethylene Polymers 0.000 claims description 8
- 239000004700 high-density polyethylene Substances 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 8
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 8
- 235000021355 Stearic acid Nutrition 0.000 claims description 7
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 claims description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 7
- 239000008117 stearic acid Substances 0.000 claims description 7
- 239000004793 Polystyrene Substances 0.000 claims description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 6
- 239000001361 adipic acid Substances 0.000 claims description 5
- 235000011037 adipic acid Nutrition 0.000 claims description 5
- 229960002446 octanoic acid Drugs 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- 235000021314 Palmitic acid Nutrition 0.000 claims description 3
- 229940057995 liquid paraffin Drugs 0.000 claims description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 3
- 229920001444 polymaleic acid Polymers 0.000 claims description 3
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 239000008400 supply water Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 8
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000005473 octanoic acid group Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Classifications
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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
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application discloses an automatic micro-crosslinking halogen-free flame-retardant thermoplastic elastomer and a preparation method thereof, wherein the thermoplastic elastomer comprises a thermoplastic elastomer main base material, reinforced resin, low molecular weight polyolefin, silane grafted polyolefin, oiling agent, inorganic flame-retardant filler and water-producing components; the inorganic flame-retardant filler reacts with the water-producing component to generate water molecules in situ to supply water molecules to the silane grafted polyolefin for hydrolysis and crosslinking to realize automatic micro-crosslinking; the acidity of the water-producing component can control the rate of generating water molecules to realize the regulation and control of micro-crosslinking rate; the proportion of the inorganic flame-retardant filler and the silane grafted polyolefin can control the micro-crosslinking degree and the flame retardant property; the carboxyl of the water-producing component and the metal ions form coordination ionic bonds to improve the interface matching of the filler and the base material and improve the dispersibility of the filler; the water producing component is one or more of long-chain fatty acid, long-chain fatty diacid and polycarboxylic acid with more than 6 carbons. The application can obviously reduce the production cost and improve the production efficiency.
Description
Technical Field
The application relates to the technical field of thermoplastic elastomers, in particular to an automatic micro-crosslinking halogen-free flame-retardant thermoplastic elastomer and a preparation method thereof.
Background
The thermoplastic elastomer has the advantages of high elasticity, ageing resistance and oil resistance of the traditional crosslinked vulcanized rubber, and convenient and abundant processing modes of common plastics, and has important application in the fields of wires, cables, plastic sports fields and the like. In recent years, people and property losses caused by combustion of common polymers in fire are striking, and how to reduce the occurrence rate of the fire and the death rate of the people in the fire is in great attention of society; in such social background, low smoke, halogen-free and flame retardant have become the main stream development direction of thermoplastic elastomer industry, and the market demand of corresponding halogen-free low smoke flame retardant thermoplastic elastomer is increasing. Technically, most of the thermoplastic elastomers are produced by adding a large amount of inorganic flame retardants such as magnesium hydroxide or aluminum hydroxide into an elastomer base material, and then carrying out melt extrusion molding, wherein the thermoplastic elastomers are required to be crosslinked under certain conditions to improve heat resistance. The addition of a large amount of inorganic flame retardant filler can seriously affect the mechanical, physical and processing properties of the material, so that the softness, weather resistance, oil resistance, low temperature resistance and the like at normal temperature are obviously deteriorated compared with the base material, in addition, the subsequent crosslinking process greatly increases the process difficulty, and simultaneously causes the environmental hazards that the thermoplastic elastomer material cannot be recycled after the service is finished.
Therefore, an automatic micro-crosslinking halogen-free flame-retardant thermoplastic elastomer capable of solving the obvious degradation of mechanical property, processability, flexibility, weather resistance, oil resistance, low temperature resistance and other properties of the thermoplastic elastomer after being filled with inorganic flame-retardant filler and a preparation process thereof are needed.
Disclosure of Invention
1. The technical problems to be solved are as follows:
aiming at the technical problems, the application provides an automatic micro-crosslinking halogen-free flame-retardant thermoplastic elastomer and a preparation method thereof, wherein inorganic flame-retardant filler reacts with water-producing components to generate water molecules in situ to supply silane grafted polyolefin to hydrolysis crosslinking action to realize automatic micro-crosslinking, the amount of the silane grafted polyolefin is controlled to adjust the micro-crosslinking degree, the acidity of the water-producing components is controlled to adjust the rate of produced water to realize the regulation of micro-crosslinking efficiency, and meanwhile, the chemical reaction of the acidic water-producing components and the flame-retardant filler solves the problem of interface matching between the filler and a base material, so that the dispersibility of the inorganic flame-retardant filler is improved.
2. The technical scheme is as follows:
an automatic micro-crosslinking halogen-free flame-retardant thermoplastic elastomer comprises a thermoplastic elastomer main base material, reinforced resin, low molecular weight polyolefin, silane grafted polyolefin, oiling agent and inorganic flame-retardant filler; the method is characterized in that: the water producing component is also included; the inorganic flame-retardant filler reacts with the water-producing component to generate water molecules in situ to supply the water molecules to the silane grafted polyolefin for hydrolysis and crosslinking to realize automatic micro-crosslinking; the acidity of the water-producing component can control the rate of generating water molecules to realize the regulation and control of micro-crosslinking rate; the proportion of the inorganic flame-retardant filler and the silane grafted polyolefin can control the micro-crosslinking degree and the flame retardant property; the carboxyl of the water-producing component and the metal ions form coordination ionic bonds to improve the interface matching of the filler and the base material and improve the dispersibility of the filler; the water producing component is one or a mixture of more than 6 long-chain fatty acid, long-chain fatty diacid and polycarboxylic acid.
Further, the metering ratio of each component is as follows: 100 parts of thermoplastic elastomer main base material, 10-30 parts of reinforced resin, 10-30 parts of low molecular weight polyolefin, 1-20 parts of silane grafted polyolefin, 10-30 parts of oiling agent, 200-300 parts of inorganic flame retardant filler and 1-10 parts of water producing component.
Further, the long-chain fatty acid with more than 6 carbons is one or more of stearic acid, palmitic acid and caprylic acid; the long-chain fatty diacid is one or a mixture of a plurality of adipic acid and normal sebacic acid; the polycarboxylic acid is polymaleic acid.
Further, the thermoplastic elastomer main base material is one or a mixture of more of SEBS and SEPS; the reinforcing resin is a mixture of one or more of PP, PS, HDPE; the low molecular weight polyolefin is one or a mixture of a plurality of low molecular weight PP, PP wax, PE and PE wax; the silane grafted polyolefin is one or a mixture of two of silane grafted polyethylene and silane grafted polypropylene; the oiling agent is one or a mixture of more of naphthenic oil, white oil, liquid paraffin and dodecylbenzene; the inorganic flame-retardant filler is one or a mixture of more of magnesium oxide, magnesium hydroxide, aluminum oxide, aluminum hydroxide and zinc oxide.
The preparation method of the automatic micro-crosslinking halogen-free flame retardant thermoplastic elastomer comprises the following steps:
step one: according to the metering ratio, the inorganic flame-retardant filler and the water-producing component are blended for a preset time at a low speed in a high-speed mixer under the normal temperature condition; adding low molecular weight polyolefin, blending for a preset time at normal temperature, and extruding and blending at a preset temperature by using a double screw to obtain inorganic flame-retardant filler master batch with a core-shell structure;
step two: mixing the thermoplastic elastomer, the reinforced resin and the oil agent according to the metering ratio at normal temperature, adding the silane grafted polyolefin and the inorganic flame-retardant filler master batch with the core-shell structure obtained in the step one, and extruding and molding after double-screw melt blending to obtain the automatic micro-crosslinking halogen-free flame-retardant thermoplastic elastomer.
Further, the first step is specifically: according to the metering ratio, the inorganic flame-retardant filler master batch with the core-shell structure is prepared by mixing inorganic flame-retardant filler and water-producing components for 1-5 min under the condition of 10-300RMP at the temperature of 20-60 ℃, adding low-molecular-weight polyolefin, continuously mixing for 1-5 min under the condition of 10-300RMP at the temperature of 20-60 ℃, and extruding and blending into granules by using double screws under the condition of 60-120 ℃.
Further, the inorganic flame-retardant filler is obtained by compounding fillers with particle sizes ranging from 0.5 to 3 mu m and two particle sizes ranging from 5 to 30 mu m; the compounding ratio of the fillers with two different particle sizes is in the range of 1:3-5 and can be adjusted.
Further, the prepared automatic micro-crosslinking halogen-free flame-retardant thermoplastic elastomer is used for cable insulation and sports fields.
3. The beneficial effects are that:
(1) According to the automatic micro-crosslinking halogen-free flame-retardant thermoplastic elastomer, the inorganic flame-retardant filler reacts with the water-producing component to generate water molecules in situ to supply the silane grafted polyolefin to the hydrolysis crosslinking action to realize automatic micro-crosslinking, so that the conventional silane crosslinking avoids the tedious and time-consuming steps of water boiling or water vapor treatment, the production cost is obviously reduced, and the production efficiency is improved; the regulation and control of the micro-crosslinking rate are realized by controlling the rate of generating water molecules by utilizing the acidity strength of the water-producing component, so that the technical problem that the conventional self-crosslinking rate is not adjustable is solved, and the application field of the product is widened. The micro-crosslinking degree and the flame retardant property are controlled by the added inorganic flame retardant filler and the silane grafted polyolefin, so that the effective regulation and control of the crosslinking degree is realized; the technical problem of interface matching of the filler and the base material is solved by utilizing the coordination ionic bond formed by the carboxyl of the acidic water-producing component and the metal ion, the dispersibility of the filler is greatly improved, and the balance of high flame retardant property and good mechanical property is well realized.
(2) According to the automatic micro-crosslinking halogen-free flame-retardant thermoplastic elastomer, the inorganic flame-retardant master batch with a core-shell structure is prepared firstly, then the base material, the reinforcing resin, the oiling agent and the like are added to prepare the automatic micro-crosslinking halogen-free flame-retardant thermoplastic elastomer, and the filler and the master batch are finally dispersed in the material in the process of secondary melt blending, so that the dispersion condition of the inorganic flame-retardant filler in a final product is remarkably improved, and the mechanical property, the stability of the performance and the comprehensive physical property of the material are further improved; the multivalent metal ions in the inorganic flame-retardant filler and the water-producing component agent form ionic bonds to play a role in compound crosslinking, so that the heat distortion temperature of the material is remarkably improved, and the application range and the field of cable materials are improved.
Detailed Description
Specific example 1:
the raw materials are as follows: 100 parts of thermoplastic elastomer main base material, 10 parts of reinforced resin, 30 parts of low molecular weight polyolefin, 1 part of silane grafted polyolefin, 30 parts of oil agent, 300 parts of inorganic flame retardant filler and 10 parts of water production component. Wherein the thermoplastic elastomer main substrate is SEPS (YH series); the reinforced resin is PP (melt fingers 1-5); the silane grafted polyolefin is silane grafted polyethylene; the oiling agent is dodecylbenzene; the low molecular weight polyolefin is low molecular weight PP; the inorganic flame-retardant filler is formed by compounding magnesium hydroxide with the particle size of about 500nm and aluminum hydroxide with the particle size of about 5 mu m, the ratio of the magnesium hydroxide to the aluminum hydroxide is 1:3, and the water-producing component is adipic acid.
The preparation method comprises the following steps:
(1) The inorganic flame-retardant filler and the water-producing component are firstly mixed for 5 min under the condition of 10 RMP at the normal temperature of 20 ℃ according to the metering ratio, low molecular weight polyolefin is added and then mixed for 5 min under the same condition, and then the mixture is extruded and blended into particles by a double screw under the condition of 120-150 ℃ to prepare the inorganic flame-retardant filler master batch with a core-shell structure.
(2) Mixing the metered thermoplastic elastomer, the reinforced resin and the oiling agent at normal temperature, adding the metered silane grafted polyolefin and the inorganic flame-retardant filler master batch with the core-shell structure obtained in the step (1), and extruding and molding after double-screw melt blending to obtain the automatic micro-crosslinking halogen-free flame-retardant thermoplastic elastomer.
Specific example 2:
the raw materials are as follows: 100 parts of thermoplastic elastomer main base material, 30 parts of reinforcing resin, 10 parts of low molecular weight polyolefin, 20 parts of silane grafted polyolefin, 10 parts of oil agent, 200 parts of inorganic flame retardant filler and 1 part of water production component. Wherein the thermoplastic elastomer main base material is SEBS; the reinforcing resin is PS; the silane grafted polyolefin is silane grafted polypropylene; the oiling agent is naphthenic oil; the low molecular weight polyolefin is PP wax; the inorganic flame-retardant filler is compounded by magnesium hydroxide with the particle size of about 1 mu m and aluminum hydroxide with the particle size of about 10 mu m, the ratio of the magnesium hydroxide to the aluminum hydroxide is 1:4, and the water-producing component is stearic acid.
The preparation method comprises the following steps:
(1) The inorganic flame-retardant filler and the water-producing component are mixed for 1min under the condition of 200RMP at the normal temperature of 60 ℃ according to the metering ratio, low molecular weight polyolefin is added and mixed for 1min under the same condition, and then the mixture is extruded and blended into particles by a double screw under the condition of 120-150 ℃ to prepare the inorganic flame-retardant filler master batch with a core-shell structure.
(2) Mixing the metered thermoplastic elastomer, the reinforced resin and the oiling agent at normal temperature, adding the metered silane grafted polyolefin and the inorganic flame-retardant filler master batch with the core-shell structure obtained in the step (1), and extruding and molding after double-screw melt blending to obtain the automatic micro-crosslinking halogen-free flame-retardant thermoplastic elastomer.
Specific example 3:
the raw materials are as follows: 100 parts of thermoplastic elastomer main base material, 20 parts of reinforcing resin, 20 parts of low molecular weight polyolefin, 10 parts of silane grafted polyolefin, 20 parts of oil agent, 250 parts of inorganic flame retardant filler and 5 parts of water production component. Wherein the thermoplastic elastomer main base materials are SEBS and SEPS (YH series), and the mass ratio of the SEBS to the SEPS is 1:1, a step of; the reinforcing resin is HDPE; the silane grafted polyolefin is silane grafted polyethylene; the oil agent is white oil; the low molecular weight polyolefin is PE; the inorganic flame-retardant filler is formed by compounding magnesium hydroxide with the particle size of about 2 mu m and aluminum hydroxide with the particle size of about 20 mu m, the ratio of the magnesium hydroxide to the aluminum hydroxide is 1:5, and the water-producing component is palmitic acid.
The preparation method comprises the following steps:
(1) The inorganic flame-retardant filler and the water-producing component are mixed for 3min under the condition of 300RMP at the normal temperature of 40 ℃ according to the metering ratio, low molecular weight polyolefin is added and mixed for 3min under the same condition, and then the mixture is extruded and blended into particles by a double screw at the temperature of 120-150 ℃ to prepare the inorganic flame-retardant filler master batch with a core-shell structure.
(2) Mixing the metered thermoplastic elastomer, the reinforced resin and the oiling agent at normal temperature, adding the metered silane grafted polyolefin and the inorganic flame-retardant filler master batch with the core-shell structure obtained in the step (1), and extruding and molding after double-screw melt blending to obtain the automatic micro-crosslinking halogen-free flame-retardant thermoplastic elastomer.
Specific example 4:
the raw materials are as follows: 100 parts of thermoplastic elastomer main base material, 20 parts of reinforcing resin, 20 parts of low molecular weight polyolefin, 10 parts of silane grafted polyolefin, 20 parts of oil agent, 250 parts of inorganic flame retardant filler and 5 parts of water production component. Wherein the thermoplastic elastomer main base materials are SEBS and SEPS (YH series), and the mass ratio of the SEBS to the SEPS is 1: 1) The method comprises the steps of carrying out a first treatment on the surface of the The reinforcing resin is HDPE; the silane grafted polyolefin is silane grafted polyethylene; the oil agent is white oil; the low molecular weight polyolefin is PE; the inorganic flame-retardant filler is compounded by magnesium hydroxide with the particle size of about 3 mu m and magnesium hydroxide with the particle size of about 30 mu m, the ratio of the magnesium hydroxide to the inorganic filler is 1:3, and the water-producing component is octanoic acid.
The preparation method comprises the following steps:
firstly mixing inorganic flame-retardant filler and water-producing components according to a metering ratio under the condition of 100RMP at the normal temperature of 30 ℃ for 4min, adding low-molecular-weight polyolefin, mixing for 4min under the same condition, and extruding and blending into particles by using a double screw under the condition of 120-150 ℃ to prepare the inorganic flame-retardant filler master batch with a core-shell structure.
(2) Mixing the metered thermoplastic elastomer, the reinforced resin and the oiling agent at normal temperature, adding the metered silane grafted polyolefin and the inorganic flame-retardant filler master batch with the core-shell structure obtained in the step (1), and extruding and molding after double-screw melt blending to obtain the automatic micro-crosslinking halogen-free flame-retardant thermoplastic elastomer. .
Specific example 5:
the raw materials are as follows: 100 parts of thermoplastic elastomer main base material, 25 parts of reinforcing resin, 15 parts of low molecular weight polyolefin, 5 parts of silane grafted polyolefin, 25 parts of oil agent, 280 parts of inorganic flame retardant filler and 7 parts of water production component. Wherein the thermoplastic elastomer main base material is prepared by mixing SEBS and SEPS (YH series), and the mass ratio is 2:1, a step of; the reinforced resin is prepared by mixing PP and HDPE, and the mass ratio is 1:1, a step of; the silane grafted polyolefin is a mixture of silane grafted polyethylene and silane grafted polypropylene, and the mass ratio of the silane grafted polyethylene to the silane grafted polypropylene is 1:1, a step of; the oiling agent is mixed by dodecylbenzene and naphthenic oil, and the mass removal ratio is 1:1; the low molecular weight polyolefin is a mixture of low molecular weight PP and PE wax, and the mass ratio of the low molecular weight PP to PE wax is 1:1, a step of; the inorganic flame-retardant filler is formed by compounding aluminum oxide with the particle size of about 800nm and zinc oxide with the particle size of about 15 mu m, the ratio of the aluminum oxide to the zinc oxide is 1:4, and the water-producing component is n-sebacic acid.
The preparation method comprises the following steps:
(1) The inorganic flame-retardant filler and the water-producing component are firstly mixed for 2min under the condition of 150RMP at the normal temperature of 50 ℃ according to the metering ratio, low molecular weight polyolefin is added and then mixed for 2min under the same condition, and then the mixture is extruded and blended into particles by a double screw under the condition of 120-150 ℃ to prepare the inorganic flame-retardant filler master batch with a core-shell structure.
(2) Mixing the metered thermoplastic elastomer, the reinforced resin and the oiling agent at normal temperature, adding the metered silane grafted polyolefin and the inorganic flame-retardant filler master batch with the core-shell structure obtained in the step (1), and extruding and molding after double-screw melt blending to obtain the automatic micro-crosslinking halogen-free flame-retardant thermoplastic elastomer. .
Specific example 6:
the raw materials are as follows: 100 parts of thermoplastic elastomer main base material, 10 parts of reinforced resin, 10 parts of low molecular weight polyolefin, 10 parts of silane grafted polyolefin, 15 parts of oil agent, 280 parts of inorganic flame retardant filler and 10 parts of water production component. Wherein the thermoplastic elastomer main substrate is SEPS (YH series); the reinforcing resin is a mixture of PS and HDPE, and the mass ratio of the reinforcing resin is 1:1, a step of; the silane grafted polyolefin is silane grafted polyethylene; the oiling agent is a mixture of dodecylbenzene and white oil, and the mass ratio of the dodecylbenzene to the white oil is 1:1, a step of; the low molecular weight polyolefin is a mixture of PP wax and PE wax, and the mass ratio of the PP wax to the PE wax is 1:1, a step of; the inorganic flame-retardant filler is formed by compounding magnesium hydroxide with the particle size of about 2.5 mu m and aluminum hydroxide with the particle size of about 20 mu m, wherein the ratio of the magnesium hydroxide to the aluminum hydroxide is 1:5, and the water-producing component is polymaleic acid with the average molecular weight of about 450.
The preparation method comprises the following steps:
(1) The inorganic flame-retardant filler and the water-producing component are firstly mixed for 2min under the condition of 250RMP at the normal temperature of 35 ℃ according to the metering ratio, the low molecular weight polyolefin is added and then mixed for 2min under the same condition, and then the mixture is extruded and blended into particles by a double screw under the condition of 120-150 ℃ to prepare the inorganic flame-retardant filler master batch with a core-shell structure.
(2) Mixing the metered thermoplastic elastomer, the reinforced resin and the oiling agent at normal temperature, adding the metered silane grafted polyolefin and the inorganic flame-retardant filler master batch with the core-shell structure obtained in the step (1), and extruding and molding after double-screw melt blending to obtain the automatic micro-crosslinking halogen-free flame-retardant thermoplastic elastomer.
Specific example 7:
the raw materials are as follows: 100 parts of thermoplastic elastomer main base material, 25 parts of reinforcing resin, 25 parts of low molecular weight polyolefin, 10 parts of silane grafted polyolefin, 10 parts of oil agent, 300 parts of inorganic flame retardant filler and 7 parts of water production component. Wherein the thermoplastic elastomer main base material is a mixture of SEBS and SEPS (YH series), and the mass ratio of the SEBS to the SEPS (YH series) is 1:2; the reinforced resin is a mixture of PP and PS, and the mass ratio of the PP to the PS is 1:2; the silane grafted polyolefin is a mixture of silane grafted polyethylene and silane grafted polypropylene, and the mass ratio of the silane grafted polyethylene to the silane grafted polypropylene is 1:2; the oil agent is prepared by mixing dodecylbenzene and liquid paraffin in a mass ratio of 1:1, a step of; the low molecular weight polyolefin is the mixture of PP and PE wax, and the mass ratio of the PP to PE wax is 1:1, a step of; the inorganic flame-retardant filler is formed by compounding magnesium hydroxide with the particle size of about 1 mu m and zinc oxide with the particle size of about 25 mu m, and the ratio of the magnesium hydroxide to the zinc oxide is 1:3.5; the water producing component is the mixture of adipic acid and stearic acid, and the mass ratio of the adipic acid to the stearic acid is 1:1.
the preparation method comprises the following steps:
(1) The inorganic flame-retardant filler and the water-producing component are firstly mixed for 3min under the condition of 200RMP at the normal temperature of 45 ℃ according to the metering ratio, low molecular weight polyolefin is added and then mixed for 3min under the same condition, and then the mixture is extruded and blended into particles by a double screw under the condition of 120-150 ℃ to prepare the inorganic flame-retardant filler master batch with a core-shell structure.
(2) Mixing the metered thermoplastic elastomer, the reinforced resin and the oiling agent at normal temperature, adding the metered silane grafted polyolefin and the inorganic flame-retardant filler master batch with the core-shell structure obtained in the step (1), and extruding and molding after double-screw melt blending to obtain the automatic micro-crosslinking halogen-free flame-retardant thermoplastic elastomer.
Specific example 8:
the raw materials are as follows: 100 parts of thermoplastic elastomer main base material, 20 parts of reinforcing resin, 25 parts of low molecular weight polyolefin, 5 parts of silane grafted polyolefin, 30 parts of oil agent, 200 parts of inorganic flame retardant filler and 5 parts of water production component. Wherein the thermoplastic elastomer main base material is SEBS; the reinforced resin is prepared by mixing PP and HDPE, and the mass ratio of the PP to the HDPE is 1:2; the silane grafted polyolefin is silane grafted polypropylene; the oiling agent is the mixture of naphthenic oil and white oil, and the mass ratio of the naphthenic oil to the white oil is 1:1, a step of; the low molecular weight polyolefin is PE wax; the inorganic flame-retardant filler is formed by compounding aluminum hydroxide with the particle size of about 1.5 mu m and zinc oxide with the particle size of about 5 mu m, and the ratio of the aluminum hydroxide to the zinc oxide is 1:4.5; the water producing component is the mixture of stearic acid and octanoic acid, and the mass ratio of the stearic acid to the octanoic acid is 1:1.
the preparation method comprises the following steps:
(1) The inorganic flame-retardant filler and the water-producing component are mixed for 1min under the condition of 300RMP at the normal temperature of 55 ℃ according to the metering ratio, low molecular weight polyolefin is added and mixed for 1min under the same condition, and then the mixture is extruded and blended into particles by a double screw under the condition of 120-150 ℃ to prepare the inorganic flame-retardant filler master batch with a core-shell structure.
(2) Mixing the metered thermoplastic elastomer, the reinforced resin and the oiling agent at normal temperature, adding the metered silane grafted polyolefin and the inorganic flame-retardant filler master batch with the core-shell structure obtained in the step (1), and extruding and molding after double-screw melt blending to obtain the automatic micro-crosslinking halogen-free flame-retardant thermoplastic elastomer.
The main technical indexes of the automatic micro-crosslinking halogen-free flame retardant thermoplastic elastomer obtained in example 2 are shown in the following table
While the application has been described with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the application, and it is intended that the scope of the application shall be defined by the appended claims.
Claims (5)
1. An automatic micro-crosslinking halogen-free flame-retardant thermoplastic elastomer comprises a thermoplastic elastomer main base material, reinforced resin, low molecular weight polyolefin, silane grafted polyolefin, oiling agent and inorganic flame-retardant filler; the method is characterized in that: the water producing component is also included; the inorganic flame-retardant filler reacts with the water-producing component to generate water molecules in situ to supply the water molecules to the silane grafted polyolefin for hydrolysis and crosslinking to realize automatic micro-crosslinking; the acidity of the water-producing component can control the rate of generating water molecules to realize the regulation and control of micro-crosslinking rate; the proportion of the inorganic flame-retardant filler and the silane grafted polyolefin can control the micro-crosslinking degree and the flame retardant property; the carboxyl of the water-producing component and the metal ions form coordination ionic bonds to improve the interface matching of the filler and the base material and improve the dispersibility of the filler; the water producing component is one or more of long-chain fatty acid with more than 6 carbons, long-chain fatty diacid and polycarboxylic acid;
the long-chain fatty acid with more than 6 carbons is one or more of stearic acid, palmitic acid and caprylic acid; the long-chain fatty diacid is one or a mixture of a plurality of adipic acid and normal sebacic acid; the polycarboxylic acid is polymaleic acid;
the thermoplastic elastomer main base material is one or a mixture of more of SEBS and SEPS; the reinforcing resin is a mixture of one or more of PP, PS, HDPE; the low molecular weight polyolefin is one or a mixture of a plurality of low molecular weight PP, PP wax, PE and PE wax; the silane grafted polyolefin is one or a mixture of two of silane grafted polyethylene and silane grafted polypropylene; the oiling agent is one or a mixture of more of naphthenic oil, white oil, liquid paraffin and dodecylbenzene; the inorganic flame-retardant filler is one or a mixture of more of magnesium oxide, magnesium hydroxide, aluminum oxide, aluminum hydroxide and zinc oxide;
the metering ratio of each component is as follows: 100 parts of thermoplastic elastomer main base material, 10-30 parts of reinforced resin, 10-30 parts of low molecular weight polyolefin, 1-20 parts of silane grafted polyolefin, 10-30 parts of oiling agent, 200-300 parts of inorganic flame retardant filler and 1-10 parts of water producing component;
preparing an automatic micro-crosslinking halogen-free flame retardant thermoplastic elastomer, which comprises the following steps:
step one: according to the metering ratio, inorganic flame retardant filler and water producing components are blended for preset time at a low speed in a high-speed mixer at 20-60 ℃; adding low molecular weight polyolefin, blending for a preset time at 20-60 ℃, and extruding and blending into particles at a preset temperature by using a double screw to obtain inorganic flame-retardant filler master batch with a core-shell structure;
step two: mixing the thermoplastic elastomer, the reinforced resin and the oil agent according to the metering ratio at normal temperature, adding the silane grafted polyolefin and the inorganic flame-retardant filler master batch with the core-shell structure obtained in the step one, and extruding and molding after double-screw melt blending to obtain the automatic micro-crosslinking halogen-free flame-retardant thermoplastic elastomer.
2. A method for preparing an automatic micro-crosslinking halogen-free flame retardant thermoplastic elastomer, which is used for preparing the automatic micro-crosslinking halogen-free flame retardant thermoplastic elastomer as claimed in claim 1, and is characterized in that: the method comprises the following steps:
step one: according to the metering ratio, inorganic flame retardant filler and water producing components are blended for preset time at a low speed in a high-speed mixer at 20-60 ℃; adding low molecular weight polyolefin, blending for a preset time at 20-60 ℃, and extruding and blending into particles at a preset temperature by using a double screw to obtain inorganic flame-retardant filler master batch with a core-shell structure;
step two: mixing the thermoplastic elastomer, the reinforced resin and the oil agent according to the metering ratio at normal temperature, adding the silane grafted polyolefin and the inorganic flame-retardant filler master batch with the core-shell structure obtained in the step one, and extruding and molding after double-screw melt blending to obtain the automatic micro-crosslinking halogen-free flame-retardant thermoplastic elastomer.
3. The method for preparing the automatic micro-crosslinking halogen-free flame retardant thermoplastic elastomer according to claim 2, which is characterized in that: the first step is as follows: according to the metering ratio of claim 2, the core-shell structure inorganic flame-retardant filler master batch is prepared by mixing inorganic flame-retardant filler and water-producing components for 1-5 min under the condition of 10-300RMP at 20-60 ℃, adding low molecular weight polyolefin, continuously mixing for 1-5 min under the condition of 10-300RMP at 20-60 ℃, and extruding and blending into granules by using a double screw at 60-120 ℃.
4. The method for preparing the automatic micro-crosslinking halogen-free flame retardant thermoplastic elastomer according to claim 2, which is characterized in that: the inorganic flame-retardant filler is obtained by compounding fillers with particle sizes ranging from 0.5 to 3 mu m and 5 to 30 mu m; the compounding ratio of the fillers with two different particle sizes is in the range of 1:3-5 and can be adjusted.
5. The method for preparing the automatic micro-crosslinking halogen-free flame retardant thermoplastic elastomer according to claim 2, which is characterized in that: the prepared automatic micro-crosslinking halogen-free flame-retardant thermoplastic elastomer is used for cable insulation and sports fields.
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