CN101570618B - Preparation method of thermotolerant high-elasticity halogen-free flame-resistant thermoplastic elastomer - Google Patents
Preparation method of thermotolerant high-elasticity halogen-free flame-resistant thermoplastic elastomer Download PDFInfo
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Abstract
The invention relates to a preparation method of a thermotolerant high-elasticity halogen-free flame-resistant thermoplastic elastomer, belonging to a preparation method of a halogen-free flame-resistant thermoplastic elastomer. The flame resistance and the mechanical property of the halogen-free flame-resistant thermoplastic elastomer can be synchronously possessed in the prior art. In the invention, inorganic flame retardant with modified surface, flame-retardant synergist having a Lewis acid and base reaction with the inorganic flame retardant, an elastomer filled with oil, thermoplastic resin, peroxide initiator, auxiliary crosslinking agent and chemical inhibitor are reacted and extruded by a double screw extruder after being mixed and stirred uniformly, thereby realizing the micro-crosslinking of the elastomer and the dispersion of the flame retardant so as to obtain the thermotolerant high-elasticity halogen-free flame-resistant thermoplastic elastomer. By the preparation method, the mechanical property, the temperature toleration and the flame resistance of the halogen-free flame-resistant thermoplastic elastomer are improved, the mechanical property of the halogen-free flame-resistant thermoplastic elastomer is about 2 times of that of the same prepared by a traditional preparation technology, the halogen-free flame-resistant thermoplastic elastomer does not deform under the temperature of 80 DEG C and is two times the conservation rate of the mechanical property of the same prepared by the traditional preparation technology after being aged for 360h under the temperature of 80 DEG C.
Description
Technical field
The present invention relates to the preparation method of halogen-free flame-retardant thermoplastic elastomer, be specifically related to a kind of preparation method of thermotolerant high-elasticity halogen-free flame-resistant thermoplastic elastomer.
Background technology
For a long time, the used fire retardant majority of flame retardant type thermoplastic elastomer is based on bromide fire retardant.But, also arguing whether will ban use of the decabromodiphynly oxide flame-retardant system in the world at present because bromide fire retardant may endanger environment in production and use always.Therefore world-renowned fire retardant production commercial city is developed the bromide fire retardant of environment-friendly type one after another, at present, there has been part decabromodiphynly oxide market to be replaced by TDE in the whole world, but because halogen flame retardant system ubiquity burning fuming amount is bigger, fire retardant is produced, use is easy to generate toxic substance, enhancing day by day along with people's awareness of safety and environmental consciousness, countries in the world are developed the Halogen novel flame redundant material one after another, the low-smoke halogen-free flame-retardant thermoplastic elastomer material of environment-friendly type is replacing traditional polyvinyl chloride and Halogen fire retardant polyolefin thermoplastic elastomer gradually, is widely used in automobile, electronic apparatus, various fields such as electric wire.
Known halogen-free flame retardant thermoplastic elastomer material preparation method directly adds halogen-free flame retardantss such as a large amount of aluminium hydroxide, magnesium hydroxide, swellability ore to make in phenylethene modified systems such as ethylene-vinyl acetate copolymer (EVA)/polyethylene (PE) modified system and hydrogenated styrene-butadiene-styrene block copolymers (SEBS)/styrene-butadiene-styrene block copolymer (SBS)/polypropylene (PP), SEBS/SBS/PE.Japanese Patent JP2001-24538 discloses with preparation halogen-free flame-retardant thermoplastic elastomers such as Thermoplastic Elastomer, Olefinic, magnesium hydroxide, inflatable stratiform ores, and the oxygen index of the halogen-free flame-retardant thermoplastic elastomer of preparation is 27.2, and elongation at break is 480.It is base material with EVA and polyethylene that Chinese patent 00122157.4 has proposed a kind of, adopts swellability graphite and the method for synergistic additive preparation halogen-free flame-retardant thermoplastic elastomer is arranged.The tensile strength of the halogen-free flame-retardant thermoplastic elastomer of this method preparation can reach 12Mpa, and elongation at break reaches 400%, and vertical combustion can pass through the UL-94V-0 level.
More than there is a lot of weak points in the preparation halogen-free flame-retardant thermoplastic elastomer, and at first, the temperature tolerance of systems such as EVA/PE, SEBS/SBS/PP, SEBS/SBS/PE is poor, is difficult to prepare the halogen-free flame-retardant thermoplastic elastomer that use temperature surpasses 80 ℃; Secondly, for making the thermoplastic elastomer of high flame retardant, must the heavy addition halogen-free flame retardants, the heavy addition of halogen-free flame retardants can make the mechanical property of thermoplastic elastomer, especially elasticity descends significantly, therefore is difficult to prepare the thermoplastic elastomer that has high flame resistance and strong mechanical performance concurrently.
Summary of the invention
The objective of the invention is to solve the problems of the prior art, and a kind of heat-resistance type, snappiness are provided and take into account excellent mechanical performances and the preparation method of the halogen-free flame-retardant thermoplastic elastomer of processing characteristics.
The key of the inventive method is: 1) extrude crosslinking technological by reaction, it is little crosslinked that thermoplastic elastomer is produced, and improves the temperature tolerance and the mechanical property of thermoplastic elastomer; 2) improve the flame retardant resistance of halogen-free flame-retardant thermoplastic elastomer by the composite flame-retardant agent of selecting to exist between fire retardant and the fire retarding synergist Lewis acid alkali reaction.Concrete steps are as follows:
1) surface modification of inorganic combustion inhibitor: with surface treatment agent and particle diameter is mixed being incorporated in more than the high-speed stirring machine high speed stirring 3min of inorganic combustion inhibitor of 1000 orders-20 nanometer, obtain the inorganic combustion inhibitor of surface modification, stir speed (S.S.) is not less than 900 rev/mins, wherein, the consumption of surface treatment agent is the 0.5%-4% of inorganic combustion inhibitor quality; If surface treatment agent is solid matter (as a stearic acid), then the surface modification process temperature should be controlled at more than the fusing point of surface treatment agent;
Adopt surface treatment agent that inorganic combustion inhibitor is carried out surface modification, thereby reduce the surface polarity of inorganic combustion inhibitor, improve the consistency of inorganic combustion inhibitor and resin matrix.
2) elastomerics is oil-filled: softening agent is mixed with elastomerics and stir, place 80 ℃ baking oven 2-3 hour, softening agent safety is held expanded in elastomerics, obtain oil-filled elastomerics, wherein, plasticizer dosage is 60%～140% of an elastomerics quality;
3) reaction is extruded crosslinked: with the inorganic combustion inhibitor of surface modification, oil-filled elastomerics, thermoplastic resin, fire retarding synergist, peroxide initiator, after additional crosslinker and the oxidation inhibitor mixing and stirring, extrude in the temperature that is higher than more than the thermoplastic resin fusing point by twin screw extruder, and underwater cutpellet, obtain the thermotolerant high-elasticity halogen-free flame-resistant thermoplastic elastomerics, wherein, thermoplastic resin and elastomeric mass ratio are 28: 72～35: 65, the consumption of inorganic combustion inhibitor is the 40%-80% of thermoplastic resin and elastomerics total mass, the mass ratio of fire retarding synergist and inorganic combustion inhibitor is 5: 95-40: 60, the consumption of peroxide initiator is the 0.05%-0.5% of elastomerics quality, and the mass ratio of additional crosslinker and peroxide initiator is 1: 2-5: 2.
Thermoplastic resin and elastomeric mass ratio can be regulated according to the hardness of desired product, and under the certain situation of plasticizer consumption, the hardness of desired product is high more, and the consumption of thermoplastic resin is high more, and elastomeric consumption is low more.
In the reaction extrusion, under the effect of peroxide initiator and additional crosslinker, it is little crosslinked that the elastomeric pair of key produces, thereby improved the thermotolerance and the elasticity of product.
Wherein, the inorganic combustion inhibitor described in the step 1) is aluminium hydroxide (Al (OH)
3) and/or magnesium hydroxide (Mg (OH)
2).
Surface treatment agent described in the step 1) is tensio-active agent or a coupling agent commonly used in the stuffing surface modification, as stearic acid, titanate coupling agent, vinyltriethoxysilane, γ-An Bingjisanyiyangjiguiwan, γ-(methacryloxy) propyl trimethoxy silicane (KH570), vinyl three (2-methoxy ethoxy) silane or γ-Qiu Jibingjisanjiayangjiguiwan.
Step 2) softening agent described in is that oil commonly used in the Rubber processing is a softening agent, comprises one or more the mixture in paraffinic oils, naphthenic oil or the perfume oil.Plasticizer dosage is regulated according to the hardness of desired product.Desired product hardness is low more, and plasticizer dosage is high more.
Step 2) elastomerics described in is the thermoplastic elastomer of the two keys of band on the molecular chain, comprises a kind of in styrene-butadiene-styrene block copolymer (SBS) or the hydrogenated styrene-butadiene-styrene block copolymers (SEBS) or the mixture of the two.
Thermoplastic resin described in the step 3) is the thermoplastic polyolefin resin, comprises one or more the blend in high density polyethylene(HDPE) (HDPE), new LDPE (film grade), linear low density polyethylene, polypropylene (PP), ethylene-propylene copolymer or the polystyrene.
Fire retarding synergist described in the step 3) be contain carboxyl, hydroxyl, amino, sulfydryl etc. can with the ultra-high molecular weight polysiloxane of the group of hydroxide radical generation Lewis acid alkali reaction in the inorganic combustion inhibitor, as acrylic acid modified dimethyl polysiloxane, ethanol modified methyl phenyl polysiloxane, amino modified tetramethyl-four benzene polysiloxane, carboxy-modified tetramethyl-four benzene polysiloxane, carboxy-modified methylvinyl-polysiloxane or sulfhydryl modified dimethyl polysiloxane.
Owing to have effective the combination between fire retarding synergist and the inorganic combustion inhibitor, further strengthened the synergy between inorganic combustion inhibitor and the fire retarding synergist, can reduce the addition of inorganic combustion inhibitor significantly, also further improved the consistency between inorganic combustion inhibitor and polymeric matrix, improve the dispersion of inorganic combustion inhibitor in thermoplastic elastomer, thereby improve the mechanical property of product.The limiting viscosity of fire retarding synergist is 10
6～10
8CSt.If the addition of fire retarding synergist is too high,, therefore can reduce the mechanical property of thermoplastic elastomer because the bond energy of fire retarding synergist self is lower.
Peroxide initiator described in the step 3) be olefin polymer grafting, degraded, crosslinked in peroxide initiator commonly used, comprise: peroxidation diisopropyl benzene (DCP), 1, two (t-butylperoxy di-isopropyl) benzene, 1 of 4-, two (t-butylperoxy di-isopropyl) benzene, 2 of 3-, 5-dimethyl-2,5-two (t-butylperoxy) hexane, 2,5-dimethyl-2,5-two (t-butylperoxy)-3-hexin, ethyl-3,3-two (t-butylperoxy) butyric ester or ethyl-3,3-two (tert-pentyl peroxy) butyric ester etc.
The peroxide initiator consumption is too high, and state of vulcanization is too high, and the flowability of product is too poor, and the consumption of peroxide initiator is too low, and the sulphidity of product is too low, the elasticity of product and poor heat resistance.
Additional crosslinker described in the step 3) is in the presence of peroxide initiator, the restriction peroxide initiator is to thermoplastic resin and elastomeric DeR, and promote peroxide initiator to elastomeric crosslinking reaction, thereby improve the polyfunctional compound of elastomeric cross-linked speed and cross-linking density, as: p-benzoqui(o)none dioxime, p or Vinylstyrene etc.
If the consumption of additional crosslinker is too low, cross-linked speed is too low, and cross-linking density is too low, and the system degraded is serious, thus the poor heat resistance of the thermoplastic elastomer that makes, poor flexibility; When the consumption of additional crosslinker is too high, cross-linked speed is too fast, and linking agent is not uniformly dispersed safely and finishes with regard to crosslinked, the quality product heterogeneity that makes.
Compared with prior art, the present invention has following beneficial effect:
1) little crosslinked in the thermoplastic elastomer of the present invention's preparation owing to producing between elastomeric molecular chain, the mechanical property and the thermotolerance of halogen-free flame-retardant thermoplastic elastomer have been improved, the mechanical property of the halogen-free flame-retardant thermoplastic elastomer of preparation is about 2 times of prior art, indeformable under 80 ℃, and just producing at 70 ℃ of the halogen-free flame-retardant thermoplastic elastomer of prior art for preparing is out of shape.
2) in the thermoplastic elastomer of the present invention preparation owing to have the Lewis acid alkali reaction between inorganic combustion inhibitor and fire retarding synergist, strengthened the synergistic effect between fire retarding synergist and inorganic combustion inhibitor, improved the flame retardant properties of halogen-free flame-retardant thermoplastic elastomer.
The invention will be further described below in conjunction with embodiment.
Embodiment
The test of the strength and extension property of halogen-free flame-retardant thermoplastic elastomer is carried out on XLL-250 type strength tester, and draw speed is 500mm/min.
The test of Static Compression deformation performance: will put into anchor clamps with the small cylindrical halogen-free flame-retardant thermoplastic elastomer TPE sample of injection molding preparation, by selected rate of compression (20%) that anchor clamps are fastening equably, make sample be compressed into the height of regulation, after parking prescribed hour under 100 ℃, take out, opening anchor clamps taking-up sample free state room temperature parked 30 minutes, measure the height of sample, calculate corresponding compression set then.
The mensuration of ageing-resistant performance: dumb-bell shape halogen-free flame-retardant thermoplastic elastomer sample is put in the 401 type ageing ovens, and temperature is controlled at 80 ℃, and digestion time is 360 hours, surveys its static mechanical performance, the multiple static mechanical property retention rate of meter.
Oxygen index (LOI) is pressed GB2406-1993 and measured: promptly under the experiment condition of regulation, halogen-free flame-retardant thermoplastic elastomer can just keep the needed limiting oxygen index concentration of state of combustion in oxygen, nitrogen mixture stream, represent with the percentage ratio of oxygen:
LOI＝[O
2]/{[O
2]+[N
2]}*100％
General oxygen index is belonging to inflammable material below 22, be nonflammable material between 22-27, is being fire retardant material more than 27.
The vertical combustion test is carried out according to GB GB2408-1996.The experimental evidence sample combustion time, whether molten drop causes test-results such as degreasing cotton, and halogen-free flame-retardant thermoplastic elastomer is decided to be V-II, V-I, V-0 level.Index is as shown in table 1:
Table 1 vertical combustion measuring technology index
Horizontal burning test is undertaken by GB2408-1996, the horizontal self-supporting of energy after one end was fixed when horizontal burning test was applicable to normal temperature, the sagging sample that is not more than 10mm of the other end, it only is used to evaluate the combustionproperty of material under the laboratory condition, can not be as the foundation of ignition hazard under the evaluation physical condition.5 samples of every group of experiment are got maximum data as the material evaluation result.The horizontal firing classification declaration is as follows:
FH-1: after removing ignition source, flame promptly goes out or fire front does not arrive the 25mm graticule;
FH-2: after removing ignition source, fire front is crossed the 25mm graticule, but does not reach the 100mm graticule;
FH-3: after removing ignition source, the burning line is crossed the 100mm graticule, and for the sample of thickness at 3-13mm, its combustionvelocity is not more than 40mm/min, and for the sample of thickness less than 3mm, its combustionvelocity is not more than 75mm/min;
FH-4: except that the regulation of linear burner speed greater than the FH-3 level, all the other are identical with the FH-3 level.
Embodiment 1
1) with 153.94g inorganic combustion inhibitor Mg (OH)
2Together add in the homogenizer with the 6.16g stearic acid, be warmed up to 80 ℃, the rotating speed high-speed stirring 5min with 900 rev/mins obtains surface modification Mg (OH)
2
2) with 166.76g SBS (trade(brand)name: SBS 1401-1, Yanshan Petrochemical provides), (SEBS 1651 for 83.39gSEBS, Kraton company provides) with 350.20g paraffin oil (trade(brand)name: PW-90) mix, in 80 ℃ baking oven, stir 2.5h, obtain the mixture of oil-filled SBS and oil-filled SEBS;
3) with the Mg (OH) of surface modification
2The mixture of oil-filled SBS and oil-filled SEBS, 134.69g polypropylene (trade(brand)name: PP 1300, Yanshan Petrochemical provides), 102.63g carboxy-modified tetramethyl-four benzene polysiloxane pellets, 0.125g dicumyl peroxide (DCP), 0.125g Vinylstyrene (DVB), 2g oxidation inhibitor (trade(brand)name: antioxidant 1010) mix, obtain mixture of raw material, it is 25 that mixture of raw material is dropped into screw diameter, length-to-diameter ratio is in 56 the twin screw extruder, rotating speed with 700r/min, react extruding pelletization down at 180 ℃, obtain the thermotolerant high-elasticity halogen-free flame-resistant thermoplastic elastomerics, performance sees Table 2.
Embodiment 2
1) with the inorganic combustion inhibitor Al (OH) of 313.72g
3Together add in the homogenizer with the titanate coupling agent of 3.14g, with 900 rev/mins rotating speed high-speed stirring 5min, obtain surface modification Al (OH) under the normal temperature
3
2) SBS 1401-1, the 63.04g SEBS 1651 with 189.11g mixes with the paraffin oil PW-90 of 252.12g, stirs 2.5h in 80 ℃ baking oven, obtains oil-filled SEBS and the mixture of oil-filled SBS;
3) with the Al (OH) of surface modification
3Oil-filled SEBS and the mixture of oil-filled SBS, 140g high density polyethylene(HDPE) (trade(brand)name: HDPE 5000S, Yanshan Petrochemical provides), 34.86g ethanol modified methyl phenyl polysiloxane, 1.26g1, two (t-butylperoxy di-isopropyl) benzene of 4-, 0.63g p-benzoqui(o)none dioxime, the 2g antioxidant 1010 mixes, obtain mixture of raw material, it is 25 that mixture of raw material is dropped into screw diameter, length-to-diameter ratio is in 56 the twin screw extruder, rotating speed with 700r/min, react extruding pelletization down at 180 ℃, obtain the thermotolerant high-elasticity halogen-free flame-resistant thermoplastic elastomerics, performance sees Table 2.
Embodiment 3
1) with the inorganic combustion inhibitor Mg (OH) of 143.09g
2Together add in the homogenizer with the KH570 of 2.87g, the rotating speed high-speed stirring 5min that normal temperature is following 900 rev/mins obtains surface modification Mg (OH)
2
2) SBS 1401-1, the 77.27g SEBS 1651 with 231.81g mixes with the paraffin oil PW-90 of 278.17g, stirs 2.5h in 80 ℃ baking oven, obtains oil-filled SEBS and the mixture of oil-filled SBS;
3) with the Mg (OH) of surface modification
2, oil-filled SEBS and mixture, the acrylic acid modified dimethyl polysiloxane of 120.20g PP 1300,143.09g, the 0.619g 1 of oil-filled SBS, two (t-butylperoxy di-isopropyl) benzene of 3-, 0.927g neighbour-phthalic acid two propylene quinones, 2g antioxidant 1010 mix, obtain mixture of raw material, with mixture of raw material drop into that screw diameter is 25, length-to-diameter ratio is in 56 the twin screw extruder, rotating speed with 700r/min, react extruding pelletization down at 180 ℃, obtain the thermotolerant high-elasticity halogen-free flame-resistant thermoplastic elastomerics, performance sees Table 2.
Embodiment 4
1) with the inorganic combustion inhibitor Mg (OH) of 275.74g
2Together add in the homogenizer with the stearic acid of 5.51g, be warming up to 80 ℃, the rotating speed high-speed stirring 5min with 900 rev/mins obtains surface modification Mg (OH)
2
2) the SBS 1401-1 with 309.56g mixes with the paraffin oil PW-90 of 185.74g, stirs 2.5h in 80 ℃ baking oven, obtains oil-filled SBS;
3) with the Mg (OH) of surface modification
2, oil-filled SBS, the carboxy-modified tetramethyl-four benzene polysiloxane of 150g PP 1300,68.94g, 1.24g DCP, 3.10g DVB, 2g antioxidant 1010 mix, obtain mixture of raw material, with mixture of raw material drop into that screw diameter is 25, length-to-diameter ratio is in 56 the twin screw extruder, rotating speed with 700r/min, react extruding pelletization down at 180 ℃, obtain the thermotolerant high-elasticity halogen-free flame-resistant thermoplastic elastomerics, performance sees Table 2.
Embodiment 5
1) with the inorganic combustion inhibitor Mg (OH) of 306.17g
2Together add in the homogenizer with the stearic acid of 6.12g, be warming up to 80 ℃, the rotating speed high-speed stirring 5min with 900 rev/mins obtains surface modification Mg (OH)
2
2) the SBS 1401-1 with 282.39g mixes with the paraffin oil PW-90 of 169.43g, stirs 2.5h in 80 ℃ baking oven, obtains oil-filled SBS;
3) with the Mg (OH) of surface modification
2, oil-filled SBS, the carboxy-modified tetramethyl-four benzene polysiloxane of 155g PP 1300,76.54g, 1.13g DCP, 1.69g DVB, 2g antioxidant 1010 mix, obtain mixture of raw material, with mixture of raw material drop into that screw diameter is 25, length-to-diameter ratio is in 56 the twin screw extruder, rotating speed with 700r/min, react extruding pelletization down at 180 ℃, obtain the thermotolerant high-elasticity halogen-free flame-resistant thermoplastic elastomerics, performance sees Table 2.
Comparative Examples 1
Employing can with the carboxy-modified tetramethyl-four benzene polysiloxane of inorganic combustion inhibitor generation Lewis acid alkali reaction as fire retarding synergist, do not add peroxide initiator and additional crosslinker, promptly do not form little crosslinkedly in the thermoplastic elastomer, concrete steps are as follows:
1) with the inorganic combustion inhibitor Mg (OH) of 153.94g
2Together add in the homogenizer with the stearic acid of 6.16g, be warmed up to 80 ℃, the rotating speed high-speed stirring 5min with 900 rev/mins obtains surface modification Mg (OH)
2
2) with the SBS (trade(brand)name: SBS 1401-1 of 166.76g, Yanshan Petrochemical provides), (SEBS 1651 for 83.39g SEBS, Kraton company provides) with the paraffin oil (trade(brand)name: PW-90) mix of 350.20g, in 80 ℃ baking oven, stir 2.5h, obtain oil-filled SBS and oil-filled SEBS mixture;
3) with above-mentioned Mg (OH) through surface modification
2, oil-filled SBS and oil-filled SEBS mixture, 134.69g polypropylene (trade(brand)name: PP 1300, Yanshan Petrochemical provides), the carboxy-modified tetramethyl-four benzene polysiloxane pellets of 102.63g, 2g oxidation inhibitor (trade(brand)name: antioxidant 1010) mix, obtain mixture of raw material, with mixture of raw material drop into that screw diameter is 25, the g length-to-diameter ratio is in 56 the twin screw extruder, rotating speed with 700r/min, react extruding pelletization down at 180 ℃, obtain halogen-free flame-retardant thermoplastic elastomer, performance sees Table 2.
Comparative Examples 2
Adopt the tetramethyl-four benzene polysiloxane that the Lewis acid alkali reaction do not take place with inorganic combustion inhibitor as fire retarding synergist, add peroxide initiator and additional crosslinker, concrete steps are as follows:
1) with the inorganic combustion inhibitor Al (OH) of 313.72g
3Together add in the homogenizer with the titanate coupling agent of 3.14g, with 900 rev/mins rotating speed high-speed stirring 5min, obtain surface modification Al (OH) under the normal temperature
3
2) SBS 1401-1, the 63.04g SEBS 1651 with 189.11g mixes with the paraffin oil PW-90 of 252.12g, stirs 2.5h in 80 ℃ baking oven, obtains oil-filled SEBS and the mixture of oil-filled SBS;
3) with the Al (OH) of surface modification
3, oil-filled SEBS and mixture, 140g HDPE 5000S, 34.86g methyl phenyl silicone, the 1.26g 1 of oil-filled SBS, two (t-butylperoxy di-isopropyl) benzene of 4-, 0.63g p-benzoqui(o)none dioxime, 2g antioxidant 1010 mix, obtain mixture of raw material, with mixture of raw material drop into that screw diameter is 25, length-to-diameter ratio is in 56 the twin screw extruder, rotating speed with 700r/min, react extruding pelletization down at 180 ℃, obtain heatproof pattern of fever high-elasticity halogen-free flame-resistant thermoplastic elastomerics, performance sees Table 2.
Comparative Examples 3
Adopt the dimethyl polysiloxane that the Lewis acid alkali reaction does not take place with inorganic combustion inhibitor as fire retarding synergist, do not add peroxide initiator and additional crosslinker, concrete steps are as follows:
1) with the inorganic combustion inhibitor Mg (OH) of 143.09g
2Together add in the homogenizer with the KH570 of 2.87g, with 900 rev/mins rotating speed high-speed stirring 5min, obtain surface modification Mg (OH) under the normal temperature
2
2) SBS 1401-1, the 77.27g SEBS 1651 with 231.81g mixes with the paraffin oil PW-90 of 278.17g, stirs 2.5h in 80 ℃ baking oven, obtains oil-filled SEBS and the mixture of oil-filled SBS;
3) with the Mg (OH) of surface modification
2, oil-filled SEBS and mixture, 120.20g PP 1300,143.09g dimethyl polysiloxane, the 2g antioxidant 1010 of oil-filled SBS mix, obtain mixture of raw material, with mixture of raw material drop into that screw diameter is 25, length-to-diameter ratio is in 56 the twin screw extruder, rotating speed with 700r/min, react extruding pelletization down at 180 ℃, obtain the thermotolerant high-elasticity halogen-free flame-resistant thermoplastic elastomerics, performance sees Table 2.
Comparative Examples 4
1) with the inorganic combustion inhibitor Mg (OH) of 275.74g
2Together add in the homogenizer with the stearic acid of 5.51g, be warming up to 80 ℃, the rotating speed high-speed stirring 5min with 900 rev/mins obtains surface modification Mg (OH)
2
2) the SBS 1401-1 with 309.56g mixes with the paraffin oil PW-90 of 185.74g, stirs 2.5h in 80 ℃ baking oven, obtains oil-filled SBS;
3) with the Mg (OH) of surface modification
2, oil-filled SBS, 150g PP 1300,68.94g tetramethyl-four benzene polysiloxane, 2g antioxidant 1010 mix, obtain mixture of raw material, with mixture of raw material drop into that screw diameter is 25, length-to-diameter ratio is in 56 the twin screw extruder, rotating speed with 700r/min, react extruding pelletization down at 180 ℃, obtain the thermotolerant high-elasticity halogen-free flame-resistant thermoplastic elastomerics, performance sees Table 2.
Comparative Examples 5
1) with the inorganic combustion inhibitor Mg (OH) of 306.17g
2Together add in the homogenizer with the stearic acid of 6.12g, be warming up to 80 ℃, the rotating speed high-speed stirring 5min with 900 rev/mins obtains surface modification Mg (OH)
2
2) the SBS 1401-1 with 282.39g mixes with the paraffin oil PW-90 of 169.43g, stirs 2.5h in 80 ℃ baking oven, obtains oil-filled SBS;
3) with the Mg (OH) of surface modification
2, oil-filled SBS, 155g PP 1300,76.54g tetramethyl-four benzene polysiloxane, 2g antioxidant 1010 mix, obtain mixture of raw material, with mixture of raw material drop into that screw diameter is 25, length-to-diameter ratio is in 56 the twin screw extruder, rotating speed with 700r/min, react extruding pelletization down at 180 ℃, obtain heat resistant type high-elasticity halogen-free flame-resistant thermoplastic elastomerics, performance sees Table 2.
The performance of table 2 halogen-free flame-retardant thermoplastic elastomer
Claims (8)
1. a preparation method of thermotolerant high-elasticity halogen-free flame-resistant thermoplastic elastomer is characterized in that, may further comprise the steps:
1) surface modification of inorganic combustion inhibitor: surface treatment agent and particle diameter are the inorganic combustion inhibitor adding stirrer for mixing of 1000 orders-20 nanometer and stir, stir speed (S.S.) is not less than 900 rev/mins, obtain the inorganic combustion inhibitor of surface modification, wherein, the consumption of surface treatment agent is the 0.5%-4% of inorganic combustion inhibitor quality;
2) elastomerics is oil-filled: softening agent is mixed with elastomerics and stir, place 80 ℃ baking oven 2-3 hour, obtain oil-filled elastomerics, plasticizer dosage is 60%～140% of an elastomerics quality;
3) reaction is extruded crosslinked: with the inorganic combustion inhibitor of surface modification, oil-filled elastomerics, thermoplastic resin, fire retarding synergist, peroxide initiator, after additional crosslinker and the oxidation inhibitor mixing and stirring, extrude in the temperature that is higher than more than the thermoplastic resin fusing point by twin screw extruder, and underwater cutpellet, obtain the thermotolerant high-elasticity halogen-free flame-resistant thermoplastic elastomerics, wherein, thermoplastic resin and elastomeric mass ratio are 28: 72～35: 65, the consumption of inorganic combustion inhibitor is the 40%-80% of thermoplastic resin and elastomerics total mass, the mass ratio of fire retarding synergist and inorganic combustion inhibitor is 5: 95-40: 60, the consumption of peroxide initiator is the 0.05%-0.5% of elastomerics quality, and the mass ratio of additional crosslinker and peroxide initiator is 1: 2-5: 2;
Above-mentioned steps 1) inorganic combustion inhibitor described in is aluminium hydroxide and/or magnesium hydroxide, the fire retarding synergist described in the step 3) be contain carboxyl, hydroxyl, amino, sulfydryl can with the ultra-high molecular weight polysiloxane of the group of hydroxide radical generation Lewis acid alkali reaction in the inorganic combustion inhibitor.
2. method according to claim 1, it is characterized in that the surface treatment agent described in the step 1) is stearic acid, titanate coupling agent, vinyltriethoxysilane, γ-An Bingjisanyiyangjiguiwan, γ-(methacryloxy) propyl trimethoxy silicane, vinyl three (2-methoxy ethoxy) silane or γ-Qiu Jibingjisanjiayangjiguiwan.
3. method according to claim 1 is characterized in that step 2) described in softening agent be one or more mixture in paraffinic oils, naphthenic oil or the perfume oil.
4. method according to claim 1 is characterized in that step 2) described in elastomerics be selected from a kind of in styrene-butadiene-styrene block copolymer or the hydrogenated styrene-butadiene-styrene block copolymers or the mixture of the two.
5. method according to claim 1, it is characterized in that the thermoplastic resin described in the step 3) is one or more the blend in high density polyethylene(HDPE), new LDPE (film grade), linear low density polyethylene, polypropylene, ethylene-propylene copolymer or the polystyrene.
6. method according to claim 1, it is characterized in that the fire retarding synergist described in the step 3) is selected from acrylic acid modified dimethyl polysiloxane, ethanol modified methyl phenyl polysiloxane, amino modified tetramethyl-four benzene polysiloxane, carboxy-modified tetramethyl-four benzene polysiloxane, carboxy-modified methylvinyl-polysiloxane or sulfhydryl modified dimethyl polysiloxane.
7. method according to claim 1, it is characterized in that, peroxide initiator described in the step 3) is selected from peroxidation diisopropyl benzene, 1, two (t-butylperoxy di-isopropyl) benzene, 1 of 4-, two (t-butylperoxy di-isopropyl) benzene, 2 of 3-, 5-dimethyl-2,5-two (t-butylperoxy) hexane, 2,5-dimethyl-2,5-two (t-butylperoxy)-3-hexin, ethyl-3,3-two (t-butylperoxy) butyric ester or ethyl-3,3-two (tert-pentyl peroxy) butyric ester.
8. method according to claim 1 is characterized in that, the additional crosslinker described in the step 3) is p-benzoqui(o)none dioxime, p or Vinylstyrene.
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| CN102477205A (en) * | 2010-11-22 | 2012-05-30 | 深圳至佳美科技有限公司 | Nano modified halogen-free wear resistant cable material and its preparation method |
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| CN103571010B (en) * | 2013-09-30 | 2016-03-02 | 芜湖航天特种电缆厂 | A kind of fireproofing cable material without halide |
| CN103601968A (en) * | 2013-10-28 | 2014-02-26 | 广东聚石化学股份有限公司 | Halogen-free flame-retardant polypropylene composite material used for making high-melt-strength sheets, and preparation method thereof |
| CN104842620A (en) * | 2014-02-18 | 2015-08-19 | 常州百佳薄膜科技有限公司 | Precipitation-resistant halogen-free flame retardation polypropylene cast sheet and production method thereof |
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| CN109535533A (en) * | 2018-11-02 | 2019-03-29 | 广东聚石化学股份有限公司 | A kind of heat resistant type low smoke and zero halogen cable material and preparation method thereof for 5G cable jacket |
| CN111234437A (en) * | 2018-11-29 | 2020-06-05 | 天长市富信电子有限公司 | Production method of thermoplastic elastomer material for signal transmission line |
| CN112592525A (en) * | 2020-12-01 | 2021-04-02 | 江苏达胜高聚物股份有限公司 | Cable sheath material and preparation method and application thereof |
| CN115109380B (en) * | 2022-08-10 | 2024-02-27 | 宁波长霖新材料有限公司 | Oil-resistant food-grade styrene thermoplastic elastomer and preparation method thereof |
| CN117143430A (en) * | 2023-10-30 | 2023-12-01 | 广州敬信高聚物科技有限公司 | Silane crosslinked TPE cable sheath material and preparation method and application thereof |
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