CN103554817A - Preparation method for anti-aging thermoplastic elastomer material applicable to textile products - Google Patents
Preparation method for anti-aging thermoplastic elastomer material applicable to textile products Download PDFInfo
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- CN103554817A CN103554817A CN201310493108.4A CN201310493108A CN103554817A CN 103554817 A CN103554817 A CN 103554817A CN 201310493108 A CN201310493108 A CN 201310493108A CN 103554817 A CN103554817 A CN 103554817A
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Abstract
The invention relates to a preparation method for an anti-aging thermoplastic elastomer material applicable to textile products. The preparation method comprises the steps: a) placing the following components in parts by weight: 15-20 parts of liquid paraffin, 10-20 parts of liquid polybutadiene, 0.5-1 part of 4-hydroxymethyl-2,6-(di-tert-butylphenol) and 0.5-1 part of sulfenyl dibutyric acid distearate into a reaction kettle for increasing temperature, adding 20-30 parts by weight of phenylacetic acid-isoprene-styrene block copolymer, and heating until all active ingredients are entirely molten; b) placing 30-40 parts by weight of hydrogenated styrene-butadiene-styrene block copolymer, vacuumizing until the hydrogenated styrene-butadiene-styrene block copolymer is entirely molten, keeping the pressure less than -0.09MPa, and stirring until no bubbles are extracted from the mixture; and c) filtering and discharging through a two-layer metal screen. The prepared thermoplastic elastomer material has good heat resistance and anti-aging properties, the physical properties cannot be greatly reduced due to overhigh temperature, and therefore, the anti-aging thermoplastic elastomer material is suitable for producing mats paved in outdoor environment.
Description
Technical field
The present invention relates to thermoplastic elastic material technical field, specifically, is a kind of preparation method who is applicable to the anti-aging thermoplastic elastic material of textile product.
Background technology
Thermoplastic elastomer (TPE, Thermo plastic Elastomer) is a kind of snappiness, high strength, high resilience with rubber, has again the material of feature that can injection molding.There is the advantages such as environment-protecting asepsis safety, tint permanence that durometer level is wide, good, soft-touch, weathering resistance, fatigue resistance and temperature tolerance are better, processing characteristics is superior, need not vulcanize, can recycle and reduce costs, both can secondary injection molding, with the body material coating and bondings such as PP, PE, PC, PS, ABS, also moulding separately.As a kind of rubber novel material of energy-conserving and environment-protective, the development prospect of thermoplastic elastic material is very good.
But the thermotolerance of thermoplastic elastic material is not as rubber, and along with temperature rising, physical property declines by a big margin, thereby the scope of application is restricted.The slipmat of for example being made by thermoplastic elastomer has that elasticity is good, good antiskid effect, toughness is good, tension force is strong, the feature of recyclable and recycling, but for outdoor use occasion, tanning by the sun for a long time of the ground cushion experience daylight in summer that thermoplastic elastic material is made, temperature is for a long time in higher state, the physical property such as its compressive set, elastic recovery can significantly decline, reduce the use sense organ of ground cushion, reduction of service life.Therefore, preparation resistance toheat is good, aging-resistant thermoplastic elastic material, for the scope of application that expands this material, promotes that popularization and energy-conserving and environment-protective are all very necessary.
Summary of the invention
The object of the invention is for deficiency of the prior art, a kind of preparation method who is applicable to the anti-aging thermoplastic elastic material of textile product is provided.
For achieving the above object, the technical scheme that the present invention takes is:
A preparation method for the anti-aging thermoplastic elastic material of textile product, comprises the following steps:
A) by weight, by whiteruss 15-20 part, liquid polybutadiene 10-20 part, 4-methylol-2,6-DI-tert-butylphenol compounds 0.5-1 part, sulfurous base two butyric acid distearyl ester 0.5-1 parts are dropped into thermal oil reactor, be warming up to 110-120 ℃, add toluylic acid-isoprene-styrene block copolymer 20-30 part, material temperature is controlled at 160-170 ℃, is heated to raw material and all melts;
B) in step a) gained mixture, drop into hydrogenated styrene-butadiene-styrene block copolymers 30-40 part, closed reactor, be less than-the 0.09Mpa that is evacuated to pressure, until hydrogenated styrene-butadiene-styrene block copolymers melts completely, keep be less than-0.09Mpa of pressure, be stirred to that mixture mixes and extract out without obvious bubble, stirring velocity is 110-120rpm, stop heating, put vacuum;
C) by double-level-metal net filtration discharging for step c) gained mixture.
Preferably, the weight ratio of described whiteruss, liquid polybutadiene, toluylic acid-isoprene-styrene block copolymer is 4: 3: 5.
Preferably, the weight ratio of described 4-methylol-2,6 di t butyl phenol and sulfurous base two butyric acid distearyl esters is 1: 1.
Preferably, the weight part of each described raw material is: 35 parts of hydrogenated styrene-butadiene-styrene block copolymers, 20 parts of whiterusss, 15 parts of liquid polybutadienes, 25 parts of toluylic acid-isoprene-styrene block copolymers, 0.8 part of 4-methylol-2,6 di t butyl phenol, 0.8 part of sulfurous base two butyric acid distearyl ester.
Preferably, the weight part of each described raw material is: 35 parts of hydrogenated styrene-butadiene-styrene block copolymers, 15 parts of whiterusss, 10 parts of liquid polybutadienes, 25 parts of toluylic acid-isoprene-styrene block copolymers, 0.8 part of 4-methylol-2,6 di t butyl phenol, 0.8 part of sulfurous base two butyric acid distearyl ester.
Preferably, the weight part of each described raw material is: 35 parts of hydrogenated styrene-butadiene-styrene block copolymers, 20 parts of whiterusss, 15 parts of liquid polybutadienes, 25 parts of toluylic acid-isoprene-styrene block copolymers, 0.6 part of 4-methylol-2,6 di t butyl phenol, 0.7 part of sulfurous base two butyric acid distearyl ester.
The invention has the advantages that:
The present invention adopts styrene-butadiene-styrene block copolymer to significantly improve the elastic resilience of thermoplastic elastic material, coupling 4-methylol-2,6-DI-tert-butylphenol compounds and sulfurous base two butyric acid distearyl esters are as antiaging agent, improved the heat-resisting and ageing resistance of the thermoplastic elastic material of preparing gained, make it can be because excess Temperature physical property significantly declines, so this material be suitable for producing the ground cushion that outdoor environment is laid.
Embodiment
Below embodiment provided by the invention is elaborated.
embodiment 1 thermoplastic elastic material preparation of the present invention (one)
(1) by weight, by 20 parts of whiterusss, 15 parts of liquid polybutadienes, 4-methylol-2,0.8 part of 6-DI-tert-butylphenol compounds, 0.8 part of input thermal oil reactor of sulfurous base two butyric acid distearyl ester, be warming up to 110-120 ℃, add 25 parts of toluylic acid-isoprene-styrene block copolymers, material temperature is controlled at 160-170 ℃, and heating 45min all melts to raw material;
(2) in step (1) gained mixture, drop into 35 parts of hydrogenated styrene-butadiene-styrene block copolymers, closed reactor, be less than-the 0.09Mpa that is evacuated to pressure, until hydrogenated styrene-butadiene-styrene block copolymers melts completely, keep be less than-0.09Mpa of pressure, stir 45min, mix and extract out without obvious bubble to mixture, stirring velocity is 115rpm, stops heating, puts vacuum;
(3) by 150 order double-level-metal net filtration dischargings for step (2) gained mixture, and adopt high temperature resistant silicone oil separate-type paper packaging final prod, must be applicable to the anti-aging thermoplastic elastic material of textile product.
embodiment 2 thermoplastic elastic material preparation of the present invention (two)
(1) by weight, by 15 parts of whiterusss, 10 parts of liquid polybutadienes, 4-methylol-2,1 part of 6-DI-tert-butylphenol compounds, 1 part of input thermal oil reactor of sulfurous base two butyric acid distearyl ester, be warming up to 110-120 ℃, add 20 parts of toluylic acid-isoprene-styrene block copolymers, material temperature is controlled at 160-170 ℃, and heating 40min all melts to raw material;
(2) in step (1) gained mixture, drop into 30 parts of hydrogenated styrene-butadiene-styrene block copolymers, closed reactor, be less than-the 0.09Mpa that is evacuated to pressure, until hydrogenated styrene-butadiene-styrene block copolymers melts completely, keep be less than-0.09Mpa of pressure, stir 50min, mix and extract out without obvious bubble to mixture, stirring velocity is 110rpm, stops heating, puts vacuum;
(3) by 150 order double-level-metal net filtration dischargings for step (2) gained mixture, and adopt high temperature resistant silicone oil separate-type paper packaging final prod, must be applicable to the anti-aging thermoplastic elastic material of textile product.
embodiment 3 thermoplastic elastic material preparation of the present invention (three)
(1) by weight, by 20 parts of whiterusss, 20 parts of liquid polybutadienes, 4-methylol-2,0.5 part of 6-DI-tert-butylphenol compounds, 0.5 part of input thermal oil reactor of sulfurous base two butyric acid distearyl ester, be warming up to 110-120 ℃, add 30 parts of toluylic acid-isoprene-styrene block copolymers, material temperature is controlled at 160-170 ℃, and heating 50min all melts to raw material;
(2) in step (1) gained mixture, drop into 40 parts of hydrogenated styrene-butadiene-styrene block copolymers, closed reactor, be less than-the 0.09Mpa that is evacuated to pressure, until hydrogenated styrene-butadiene-styrene block copolymers melts completely, keep be less than-0.09Mpa of pressure, stir 40min, mix and extract out without obvious bubble to mixture, stirring velocity is 120rpm, stops heating, puts vacuum;
(3) by 150 order double-level-metal net filtration dischargings for step (2) gained mixture, and adopt high temperature resistant silicone oil separate-type paper packaging final prod, must be applicable to the anti-aging thermoplastic elastic material of textile product.
embodiment 4 thermoplastic elastic material preparation of the present invention (four)
(1) by weight, by 15 parts of whiterusss, 10 parts of liquid polybutadienes, 4-methylol-2,0.8 part of 6-DI-tert-butylphenol compounds, 0.8 part of input thermal oil reactor of sulfurous base two butyric acid distearyl ester, be warming up to 110-120 ℃, add 25 parts of toluylic acid-isoprene-styrene block copolymers, material temperature is controlled at 160-170 ℃, and heating 40min all melts to raw material;
(2) in step (1) gained mixture, drop into 35 parts of hydrogenated styrene-butadiene-styrene block copolymers, closed reactor, be less than-the 0.09Mpa that is evacuated to pressure, until hydrogenated styrene-butadiene-styrene block copolymers melts completely, keep be less than-0.09Mpa of pressure, stir 50min, mix and extract out without obvious bubble to mixture, stirring velocity is 110rpm, stops heating, puts vacuum;
(3) by 150 order double-level-metal net filtration dischargings for step (2) gained mixture, and adopt high temperature resistant silicone oil separate-type paper packaging final prod, must be applicable to the anti-aging thermoplastic elastic material of textile product.
embodiment 5 thermoplastic elastic material preparation of the present invention (five)
(1) by weight, by 20 parts of whiterusss, 15 parts of liquid polybutadienes, 4-methylol-2,0.6 part of 6-DI-tert-butylphenol compounds, 0.7 part of input thermal oil reactor of sulfurous base two butyric acid distearyl ester, be warming up to 110-120 ℃, add 25 parts of toluylic acid-isoprene-styrene block copolymers, material temperature is controlled at 160-170 ℃, and heating 50min all melts to raw material;
(2) in step (1) gained mixture, drop into 35 parts of hydrogenated styrene-butadiene-styrene block copolymers, closed reactor, be less than-the 0.09Mpa that is evacuated to pressure, until hydrogenated styrene-butadiene-styrene block copolymers melts completely, keep be less than-0.09Mpa of pressure, stir 40min, mix and extract out without obvious bubble to mixture, stirring velocity is 120rpm, stops heating, puts vacuum;
(3) by 150 order double-level-metal net filtration dischargings for step (2) gained mixture, and adopt high temperature resistant silicone oil separate-type paper packaging final prod, must be applicable to the anti-aging thermoplastic elastic material of textile product.
embodiment 6 thermoplastic elastic material preparation of the present invention (six)
(1) by weight, by 15 parts of whiterusss, 20 parts of liquid polybutadienes, 4-methylol-2,0.5 part of 6-DI-tert-butylphenol compounds, 1 part of input thermal oil reactor of sulfurous base two butyric acid distearyl ester, be warming up to 110-120 ℃, add 20 parts of toluylic acid-isoprene-styrene block copolymers, material temperature is controlled at 160-170 ℃, and heating 45min all melts to raw material;
(2) in step (1) gained mixture, drop into 40 parts of hydrogenated styrene-butadiene-styrene block copolymers, closed reactor, be less than-the 0.09Mpa that is evacuated to pressure, until hydrogenated styrene-butadiene-styrene block copolymers melts completely, keep be less than-0.09Mpa of pressure, stir 50min, mix and extract out without obvious bubble to mixture, stirring velocity is 115rpm, stops heating, puts vacuum;
(3) by 150 order double-level-metal net filtration dischargings for step (2) gained mixture, and adopt high temperature resistant silicone oil separate-type paper packaging final prod, must be applicable to the anti-aging thermoplastic elastic material of textile product.
comparative example 1
(1) by weight, by 30 parts of whiterusss, 20 parts of liquid polybutadienes, 4-methylol-2,0.8 part of 6-DI-tert-butylphenol compounds, 0.8 part of input thermal oil reactor of sulfurous base two butyric acid distearyl ester, be warming up to 160-170 ℃, material temperature is controlled at 160-170 ℃, and heating 45min all melts to raw material;
(2) in step (1) gained mixture, drop into 45 parts of hydrogenated styrene-butadiene-styrene block copolymers, closed reactor, be less than-the 0.09Mpa that is evacuated to pressure, until hydrogenated styrene-butadiene-styrene block copolymers melts completely, keep be less than-0.09Mpa of pressure, stir 45min, mix and extract out without obvious bubble to mixture, stirring velocity is 115rpm, stops heating, puts vacuum;
(3) by 150 order double-level-metal net filtration dischargings for step (2) gained mixture, and adopt high temperature resistant silicone oil separate-type paper packaging final prod, obtain thermoplastic elastic material.
comparative example 2
(1) by weight, by 15 parts of whiterusss, 10 parts of liquid polybutadienes, 4-methylol-2,1 part of 6-DI-tert-butylphenol compounds, 1.2 parts of input thermal oil reactors of sulfurous base two butyric acid distearyl ester, be warming up to 110-120 ℃, add 20 parts of toluylic acid-isoprene-styrene block copolymers, material temperature is controlled at 160-170 ℃, and heating 40min all melts to raw material;
(2) in step (1) gained mixture, drop into 30 parts of hydrogenated styrene-butadiene-styrene block copolymers, closed reactor, be less than-the 0.09Mpa that is evacuated to pressure, until hydrogenated styrene-butadiene-styrene block copolymers melts completely, keep be less than-0.09Mpa of pressure, stir 50min, mix and extract out without obvious bubble to mixture, stirring velocity is 110rpm, stops heating, puts vacuum;
(3) by 150 order double-level-metal net filtration dischargings for step (2) gained mixture, and adopt high temperature resistant silicone oil separate-type paper packaging final prod, obtain thermoplastic elastic material.
comparative example 3
(1) by weight, by 20 parts of whiterusss, 20 parts of liquid polybutadienes, 4-methylol-2,0.5 part of 6-DI-tert-butylphenol compounds, 0.4 part of input thermal oil reactor of sulfurous base two butyric acid distearyl ester, be warming up to 110-120 ℃, add 30 parts of toluylic acid-isoprene-styrene block copolymers, material temperature is controlled at 160-170 ℃, and heating 50min all melts to raw material;
(2) in step (1) gained mixture, drop into 40 parts of hydrogenated styrene-butadiene-styrene block copolymers, closed reactor, be less than-the 0.09Mpa that is evacuated to pressure, until hydrogenated styrene-butadiene-styrene block copolymers melts completely, keep be less than-0.09Mpa of pressure, stir 40min, mix and extract out without obvious bubble to mixture, stirring velocity is 120rpm, stops heating, puts vacuum;
(3) by 150 order double-level-metal net filtration dischargings for step (2) gained mixture, and adopt high temperature resistant silicone oil separate-type paper packaging final prod, obtain thermoplastic elastic material.
comparative example 4
(1) by weight, by 20 parts of whiterusss, 15 parts of liquid polybutadienes, 1.6 parts of input thermal oil reactors of sulfurous base two butyric acid distearyl ester, be warming up to 110-120 ℃, add 25 parts of toluylic acid-isoprene-styrene block copolymers, material temperature is controlled at 160-170 ℃, and heating 45min all melts to raw material;
(2) in step (1) gained mixture, drop into 35 parts of hydrogenated styrene-butadiene-styrene block copolymers, closed reactor, be less than-the 0.09Mpa that is evacuated to pressure, until hydrogenated styrene-butadiene-styrene block copolymers melts completely, keep be less than-0.09Mpa of pressure, stir 45min, mix and extract out without obvious bubble to mixture, stirring velocity is 115rpm, stops heating, puts vacuum;
(3) by 150 order double-level-metal net filtration dischargings for step (2) gained mixture, and adopt high temperature resistant silicone oil separate-type paper packaging final prod, obtain thermoplastic elastic material.
comparative example 5
(1) by weight, by 20 parts of whiterusss, 15 parts of liquid polybutadienes, 4-methylol-2,1.6 parts of input thermal oil reactors of 6-DI-tert-butylphenol compounds, be warming up to 110-120 ℃, add 25 parts of toluylic acid-isoprene-styrene block copolymers, material temperature is controlled at 160-170 ℃, and heating 45min all melts to raw material;
(2) in step (1) gained mixture, drop into 35 parts of hydrogenated styrene-butadiene-styrene block copolymers, closed reactor, be less than-the 0.09Mpa that is evacuated to pressure, until hydrogenated styrene-butadiene-styrene block copolymers melts completely, keep be less than-0.09Mpa of pressure, stir 45min, mix and extract out without obvious bubble to mixture, stirring velocity is 115rpm, stops heating, puts vacuum;
(3) by 150 order double-level-metal net filtration dischargings for step (2) gained mixture, and adopt high temperature resistant silicone oil separate-type paper packaging final prod, obtain thermoplastic elastic material.
embodiment 7 performance tests
The main performance index of thermoplastic elastic material prepared by embodiment 1-6 and comparative example 1-5 is tested, and testing standard is with reference to GB/T1040-2006, and result is as shown in table 1.The present invention adopts styrene-butadiene-styrene block copolymer can significantly improve the elastic resilience of thermoplastic elastic material, used 4-methylol-2,6-DI-tert-butylphenol compounds and sulfurous base two butyric acid distearyl esters, jointly as antiaging agent, can guarantee that thermoplastic elastic material can significantly not decline because of excess Temperature physical property.Research is discovery also, and when the weight ratio of raw material liq paraffin, liquid polybutadiene, toluylic acid-isoprene-styrene block copolymer is 4: 3: 5, material thermal resistance and the ageing resistance of preparation are better; Antiaging agent 4-methylol-2, the weight ratio of 6-DI-tert-butylphenol compounds and sulfurous base two butyric acid distearyl esters is 1: 1 o'clock, contribution for material thermal resistance and ageing resistance is more obvious, and 4-methylol-2,6 di t butyl phenol and sulfurous base two butyric acid distearyl esters should couplings; And in raw material, base-material and ageing-resistant ratio are preferably controlled within the scope of the invention.Thermoplastic elastic material thermotolerance of the present invention, ageing resistance are better, are suitable for producing the ground cushion that outdoor environment is laid.
The main performance index of thermoplastic elastic material prepared by table 1 embodiment 1-6 and comparative example 1-5
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, do not departing under the prerequisite of the inventive method; can also make some improvement and supplement, these improvement and supplement and also should be considered as protection scope of the present invention.
Claims (6)
1. a preparation method who is applicable to the anti-aging thermoplastic elastic material of textile product, is characterized in that, comprises the following steps:
A) by weight, by whiteruss 15-20 part, liquid polybutadiene 10-20 part, 4-methylol-2,6-DI-tert-butylphenol compounds 0.5-1 part, sulfurous base two butyric acid distearyl ester 0.5-1 parts are dropped into thermal oil reactor, be warming up to 110-120 ℃, add toluylic acid-isoprene-styrene block copolymer 20-30 part, material temperature is controlled at 160-170 ℃, is heated to raw material and all melts;
B) in step a) gained mixture, drop into hydrogenated styrene-butadiene-styrene block copolymers 30-40 part, closed reactor, be less than-the 0.09Mpa that is evacuated to pressure, until hydrogenated styrene-butadiene-styrene block copolymers melts completely, keep be less than-0.09Mpa of pressure, be stirred to that mixture mixes and extract out without obvious bubble, stirring velocity is 110-120rpm, stop heating, put vacuum;
C) by double-level-metal net filtration discharging for step c) gained mixture.
2. preparation method according to claim 1, is characterized in that, the weight ratio of described whiteruss, liquid polybutadiene, toluylic acid-isoprene-styrene block copolymer is 4: 3: 5.
3. preparation method according to claim 1, is characterized in that, the weight ratio of described 4-methylol-2,6 di t butyl phenol and sulfurous base two butyric acid distearyl esters is 1: 1.
4. preparation method according to claim 1, it is characterized in that, the weight part of each described raw material is: 35 parts of hydrogenated styrene-butadiene-styrene block copolymers, 20 parts of whiterusss, 15 parts of liquid polybutadienes, 25 parts of toluylic acid-isoprene-styrene block copolymers, 0.8 part of 4-methylol-2,6 di t butyl phenol, 0.8 part of sulfurous base two butyric acid distearyl ester.
5. preparation method according to claim 1, it is characterized in that, the weight part of each described raw material is: 35 parts of hydrogenated styrene-butadiene-styrene block copolymers, 15 parts of whiterusss, 10 parts of liquid polybutadienes, 25 parts of toluylic acid-isoprene-styrene block copolymers, 0.8 part of 4-methylol-2,6 di t butyl phenol, 0.8 part of sulfurous base two butyric acid distearyl ester.
6. preparation method according to claim 1, it is characterized in that, the weight part of each described raw material is: 35 parts of hydrogenated styrene-butadiene-styrene block copolymers, 20 parts of whiterusss, 15 parts of liquid polybutadienes, 25 parts of toluylic acid-isoprene-styrene block copolymers, 0.6 part of 4-methylol-2,6 di t butyl phenol, 0.7 part of sulfurous base two butyric acid distearyl ester.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030125434A1 (en) * | 2001-12-31 | 2003-07-03 | Mattel, Inc. | High molecuar weight styrenic block copolymer hot melt adhesive for toy articles |
| CN1822948A (en) * | 2003-05-15 | 2006-08-23 | 旭化成化学株式会社 | Laminates containing hydrogenated copolymers |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030125434A1 (en) * | 2001-12-31 | 2003-07-03 | Mattel, Inc. | High molecuar weight styrenic block copolymer hot melt adhesive for toy articles |
| CN1822948A (en) * | 2003-05-15 | 2006-08-23 | 旭化成化学株式会社 | Laminates containing hydrogenated copolymers |
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Application publication date: 20140205 |