CN106700385A - Stress-whitening-resisting modified styrene-based resin and preparation method thereof - Google Patents
Stress-whitening-resisting modified styrene-based resin and preparation method thereof Download PDFInfo
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- CN106700385A CN106700385A CN201510778945.0A CN201510778945A CN106700385A CN 106700385 A CN106700385 A CN 106700385A CN 201510778945 A CN201510778945 A CN 201510778945A CN 106700385 A CN106700385 A CN 106700385A
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- modified styrene
- resin
- proof stress
- acid
- turns white
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Abstract
The invention provides stress-whitening-resisting modified styrene-based resin and a preparation method thereof. The stress-whitening-resisting modified styrene-based resin is prepared from, by weight, 80-98 parts of styrene-based resin, 2-20 parts of superfine talcum powder, 0.1-1 part of photo-thermal stabilizer and 0.1-1 part of lubricant through mixing and extrusion pelleting. The grain size of the superfine talcum powder ranges from 6,000 mesh to 7,000 mesh. The prepared material is good in mechanical performance and has the advantages of being easy to process and form and the like, especially the stress-whitening-resisting phenomenon of the material is controlled, and the material can be used for the product occasion that various materials required to keep the appearances and the like under the condition of bearing external force many times are formed.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to modified styrene resin that a kind of proof stress turns white and preparation method thereof.
Background technology
Styrene base resin is a kind of extremely conventional macromolecular material; its range of application is widely; but its product is such as stretched, bends, impacting the phenomenon that White Patches often occur when external force is acted on, that is, the stress whitening described in us in use.Product not only influences its outward appearance after there is stress whitening phenomenon, and can cause the reduction of product elongation at break, intensity decreases and stress crack resistance performance variation etc., and product can be influenceed to use when serious.Relatively conventional in the stress white hair solution of styrene base resin product at present is to be heat-treated product, will product be placed under certain temperature conditionss to be post-processed and eliminate its internal stress.But when the method is more complicated for product this body structure, then internal stress eradicating efficacy is just relatively more general.
The content of the invention
Modified styrene resin that a kind of proof stress turns white and preparation method thereof is provided the present invention be directed to the defect of prior art.The features such as material has function admirable, machine-shaping is good, it is important that material preparation method is simple, production efficiency is high, can be used to be often subject to the occasion of external force simultaneously, be effectively reduced and avoid the generation of stress whitening phenomenon, expand the application field of styrene base resin material.
To achieve the above object, the technical solution adopted by the present invention is as follows：
A kind of modified styrene resin that proof stress turns white, the material is prepared from by weight by following components：
Styrene base resin
80~98 parts,
Superfine talcum powder
2~20 parts,
Optothermal stabilizer
0.1~1 part,
Lubricant
0.1~1 part,
The particle diameter of the superfine talcum powder is 6000-7000 mesh.
Further scheme, described styrene base resin includes acrylonitrile-butadiene-phenylethene grafted copolymer（ABS）, MBS graft copolymer（MBS）, acrylonitrile-styrene-acrylic ternary copolymer（ASA）In at least one.
Described acrylonitrile-butadiene-phenylethene grafted copolymer（ABS）Resin refers to the ABS resin of substance law synthesis, wherein continuous phase acrylonitrile content >=25%, and melt index is 10-35g/10min under the conditions of 220 DEG C/10Kg.
Described optothermal stabilizer be selected from monothioester type thermal stabilizing agent, organic tin heat stabilizer, hindered amine, hindered phenol, diphenyl phosphite or triphenyl phosphite in one or more.
It is double that described monothioester type thermal stabilizing agent is selected from thio-2 acid（Lauryl alcohol）Ester, thio-2 acid two（Octadecyl alcolol）Ester, thio-2 acid two（Tridecanol）Ester or thio-2 acid two（Tetradecyl alchohol）Ester；
Described organic tin heat stabilizer is selected from pink salt containing mercaptan, maleic acid pink salt or pant tin carboxylate；
Described hindered amine is selected from naphthylamines, diphenylamines or p-phenylenediamine；
Described hindered phenol is selected from 2,6- three-level butyl -4- methylphenols, double（3,5- three-level butyl -4- hydroxy phenyls）Thioether or four (β-(3,5- three-level butyl -4- hydroxy phenyls) propionic acid) pentaerythritol esters.
The preferred dimercapto 2-ethyl hexyl ethanoate dioctyltin of described pink salt containing mercaptan or dimethyl dimercapto 2-ethyl hexyl ethanoate tin；
Described maleic acid pink salt is selected from maleic acid di-n-butyl tin；
Described pant tin carboxylate is selected from di-n-butyltin dilaurate or Bis(lauroyloxy)dioctyltin.
Described lubricant is selected from solid paraffin, atoleine, stearic amide, methylene bis stearic amide, N, at least one in N- ethylene bis stearic acid amides or silicone oil.
Another goal of the invention of the invention is to provide the preparation method of the modified styrene resin that above-mentioned proof stress turns white, and comprises the following steps：
（1）By 80~98 parts of styrene base resin, superfine talcum powder 2-20 parts, 0.1~1 part of 0.1~1 part of optothermal stabilizer and lubricant are well mixed；
（2）By extruding pelletization in mixed material addition double screw extruder, styrene base resin material is obtained；The double-screw extruder screw temperature is 200~240 DEG C；Screw speed is in 100~500 r/min.
The step（2）Middle screw speed is 400~500 r/min.
The present invention compared with the existing technology, has the advantages that：
1st, the present invention prepares styrene base resin using twin screw extrusion process, has the advantages that flow is simple, continuous, production efficiency is high, product quality is stable.
2nd, preferably, the features such as shaping with easy processing, especially the proof stress blushing of material is controlled the mechanical property of the prepared material of the present invention, can be used for shaping various requirement material and the product occasions such as outward appearance are kept in the case of repeatedly by external force.
3rd, the proof stress styrene base resin that turns white that prepared by the present invention can be used for the product scope of shades of colour and other modified purposes.
4th, the present invention selects superfine talcum powder, can be easily combined into styrene base resin " island structure " because its activity is higher, resin can be absorbed can be produced crazing when being acted on by external force and generate a large amount of small crackles, the further development of crackle is prevented, and then can slow down or prevent the stress whitening phenomenon of styrene base resin.
Specific embodiment
The present invention is further illustrated with reference to embodiments.
The quantitative measurement standard of the modified styrene resin that the proof stress prepared by the present invention turns white is shown in Table 1.
Wherein proof stress turns white performance test methods：It is that size is the plastics square plate of 250mm*200mm*2mm by material injection, 500g steel balls fall from 1 meter of height and pound onto plastics square plate, see the apparent state of blush of model；
Stress crack resistance performance method of testing：Material is molded into dumbbell shape batten by ASTM D638, is bent with fixed angle, and fix its two ends, glacial acetic acid or acetone are smeared in its stress raiser, observation is by solvent etched to the time and state ftractureed.
ABS resin is the graft copolymer of acrylonitrile-butadiene-styrene (ABS) prepared by Shanghai Gaoqiao petrochemical industry substance law（Such as trade mark ABS 8434）；
Acrylonitrile-styrene-acrylic ternary copolymer（ASA, Taiwan is strange, ASA PW-957）；
MBS graft copolymer（MBS, LG company, MBS TR-557）.
Optothermal stabilizer is Hinered phenols antioxidant, antioxidant 1076 be the Irganox1076 β of CIBA-（3,5- di-tert-butyl-hydroxy phenyls）The positive octadecanol ester of propionic acid）With the Irganox168 that irgasfos 168 is phosphite ester kind antioxidant CIBA（Three ［ 2.4- di-tert-butyl-phenyls ］ phosphite esters）, thio-2 acid two（Lauryl alcohol）Ester（DLTP）, 2,6- three-level butyl -4- methylphenols, di-n-butyltin dilaurate (DBTL), maleic acid di-n-butyl tin (DBTM), Bis(lauroyloxy)dioctyltin (DOTL) or dimercapto 2-ethyl hexyl ethanoate dioctyltin (DOTTG).
Lubricant is solid paraffin, atoleine, stearic amide（SR）, silicone oil or N, N- ethylene bis stearic acid amide（EBS）.
Embodiment
1
（1）By 85 parts of resins of ABS 8434,15 parts of superfine talcum powders（6000 mesh）, 0.3 part of optothermal stabilizer（Antioxidant 1076：Irgasfos 168=1：2, mass ratio）And 0.1 part of lubricant stearic acid acid amides（SR）It is well mixed through high-speed stirred；
（2）By extruding pelletization in said mixture feeding double screw extruder, styrene base resin is obtained；
Described step（2）Middle double-screw extruder screw temperature is 400
r/min。
The compound of preparation is molded into the standard batten of test by standard size, and the performance test results are as shown in table 2.
Embodiment
2
（1）By 98 parts of ABS8434 and the mixture of ASA PW-957 resins（ABS8434：ASA PW-957=2：1, mass ratio）, 2 parts of superfine talcum powders（7000 mesh）, 0.6 part of optothermal stabilizer（Anti-oxidant DLTP：Antioxidant DBTL=1：1, mass ratio）And 0.5 part of lubricant silicone oil is well mixed through high-speed stirred；
（2）By extruding pelletization in said mixture feeding double screw extruder, styrene base resin is obtained；
Described step（2）Middle double-screw extruder screw temperature is 500
r/min。
The compound of preparation is molded into the standard batten of test by standard size, and the performance test results are as shown in table 2.
Embodiment
3
（1）By 90 parts of ASA PW-957 resins, 10 parts of superfine talcum powders（6000 mesh）, 0.1 part of optothermal stabilizer（DLTP：2,6- three-level butyl -4- methylphenol=2：1, mass ratio）And 1 part of Lubricate EBS is well mixed through high-speed stirred；
（2）By extruding pelletization in said mixture feeding double screw extruder, styrene base resin is obtained；
Described step（2）Middle double-screw extruder screw temperature is 300
r/min。
The compound of preparation is molded into the standard batten of test by standard size, and the performance test results are as shown in table 2.
Embodiment
4
（1）By 95 parts of MBS TR-557 resins, 5 parts of superfine talcum powders（7000 mesh）Resin, 0.6 part of optothermal stabilizer（DBTL：DBTM=1：1, mass ratio）And 0.5 part of lubricant solids paraffin and atoleine（Mass ratio 1：1）It is well mixed through high-speed stirred；
（2）By extruding pelletization in said mixture feeding double screw extruder, styrene base resin is obtained；
Described step（2）Middle double-screw extruder screw temperature is 200
r/min。
The compound of preparation is molded into the standard batten of test by standard size, and the performance test results are as shown in table 2.
Embodiment
5
（1）By 80 parts of ABS8434 resins, 20 parts of superfine talcum powders（6000 mesh）, 1 part of optothermal stabilizer（DOTL：DOTTG=1：2, mass ratio）And 0.6 part of lubricant silicone oil is well mixed through high-speed stirred；
（2）By extruding pelletization in said mixture feeding double screw extruder, styrene base resin is obtained；
Described step（2）Middle double-screw extruder screw temperature is 100
r/min。
The compound of preparation is molded into the standard batten of test by standard size, and the performance test results are as shown in table 2.
Comparative example
ABS8434 resins are directly molded into the standard batten of test by standard size, the performance test results are as shown in table 2.
As can be seen from Table 2, quite, but the styrene base resin mechanical strength for preparing of the present invention is apparently higher than the mechanical strength of existing unmodified ABS resin for the density of the ABS resin in proof stress the modified styrene resin and comparative example that turn white prepared by embodiment of the present invention 1-5；And the stress-whitening resistance energy of styrene base resin can be significantly improved, it is used in the multiple stress occasion required to mechanical property, appearance property etc..
The above-mentioned description to embodiment is to be understood that and apply the present invention for ease of those skilled in the art.Person skilled in the art obviously can easily make various modifications to these embodiments, and General Principle described herein is applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art's announcement of the invention, does not depart from improvement that scope made and modification all should be within protection scope of the present invention.
Claims (9)
1. the modified styrene resin that a kind of proof stress turns white, it is characterised in that：It is prepared from by weight by following components：
80~98 parts of styrene base resin,
2~20 parts of superfine talcum powder,
Optothermal stabilizer
0.1~1 part,
Lubricant
0.1~1 part,
The particle diameter of the superfine talcum powder is 6000-7000 mesh.
2. the modified styrene resin that a kind of proof stress according to claim 1 turns white, it is characterised in that：Described styrene base resin includes at least one in acrylonitrile-butadiene-phenylethene grafted copolymer, MBS graft copolymer or acrylonitrile-styrene-acrylic ternary copolymer.
3. the modified styrene resin that a kind of proof stress according to claim 2 turns white, it is characterised in that：Described acrylonitrile-butadiene-phenylethene grafted copolymer resin refers to the ABS resin of substance law synthesis, wherein continuous phase acrylonitrile content >=25%, and melt index is 10-35g/10min under the conditions of 220 DEG C/10Kg.
4. the modified styrene resin that a kind of proof stress according to claim 1 turns white, it is characterised in that：Described optothermal stabilizer be selected from monothioester type thermal stabilizing agent, organic tin heat stabilizer, hindered amine, hindered phenol, diphenyl phosphite or triphenyl phosphite in one or more.
5. the modified styrene resin that a kind of proof stress according to claim 4 turns white, it is characterised in that：It is double that described monothioester type thermal stabilizing agent is selected from thio-2 acid（Lauryl alcohol）Ester, thio-2 acid two（Octadecyl alcolol）Ester, thio-2 acid two（Tridecanol）Ester or thio-2 acid two（Tetradecyl alchohol）Ester；
Described organic tin heat stabilizer is selected from pink salt containing mercaptan, maleic acid pink salt or pant tin carboxylate；
Described hindered amine is selected from naphthylamines, diphenylamines or p-phenylenediamine；
Described hindered phenol is selected from 2,6- three-level butyl -4- methylphenols, double（3,5- three-level butyl -4- hydroxy phenyls）Thioether or four (β-(3,5- three-level butyl -4- hydroxy phenyls) propionic acid) pentaerythritol esters.
6. the modified styrene resin that a kind of proof stress according to claim 5 turns white, it is characterised in that：The preferred dimercapto 2-ethyl hexyl ethanoate dioctyltin of described pink salt containing mercaptan or dimethyl dimercapto 2-ethyl hexyl ethanoate tin；
Described maleic acid pink salt is selected from maleic acid di-n-butyl tin；
Described pant tin carboxylate is selected from di-n-butyltin dilaurate or Bis(lauroyloxy)dioctyltin.
7. the modified styrene resin that a kind of proof stress according to claim 1 turns white, it is characterised in that：Described lubricant is selected from solid paraffin, atoleine, stearic amide, methylene bis stearic amide, N, at least one in N- ethylene bis stearic acid amides or silicone oil.
8. the preparation method of the modified styrene resin that a kind of proof stress as claimed in claim 1 turns white, it is characterised in that：Comprise the following steps：
（1）By 80~98 parts of styrene base resin, superfine talcum powder 2-20 parts, 0.1~1 part of 0.1~1 part of optothermal stabilizer and lubricant are well mixed；
（2）By extruding pelletization in mixed material addition double screw extruder, styrene base resin material is obtained；The double-screw extruder screw temperature is 200~240 DEG C；Screw speed is in 100~500 r/min.
9. preparation method according to claim 8, it is characterised in that：The step（2）Middle screw speed is 400~500 r/min.
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|---|---|---|---|
| CN201510778945.0A CN106700385A (en) | 2015-11-15 | 2015-11-15 | Stress-whitening-resisting modified styrene-based resin and preparation method thereof |
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| CN201510778945.0A CN106700385A (en) | 2015-11-15 | 2015-11-15 | Stress-whitening-resisting modified styrene-based resin and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103602028A (en) * | 2013-10-24 | 2014-02-26 | 合肥会通新材料有限公司 | Injection-molding-grade foaming ABS material and preparation method thereof |
| CN103756240A (en) * | 2013-12-30 | 2014-04-30 | 天津金发新材料有限公司 | Stress whitening resistance ABS (Acrylonitrile Butadiene Styrene) composite material as well as preparation method and application thereof |
| CN104072869A (en) * | 2014-06-20 | 2014-10-01 | 上海俊尓新材料有限公司 | Stress whitening resisting modified polypropylene material as well as preparation method and application thereof |
-
2015
- 2015-11-15 CN CN201510778945.0A patent/CN106700385A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103602028A (en) * | 2013-10-24 | 2014-02-26 | 合肥会通新材料有限公司 | Injection-molding-grade foaming ABS material and preparation method thereof |
| CN103756240A (en) * | 2013-12-30 | 2014-04-30 | 天津金发新材料有限公司 | Stress whitening resistance ABS (Acrylonitrile Butadiene Styrene) composite material as well as preparation method and application thereof |
| CN104072869A (en) * | 2014-06-20 | 2014-10-01 | 上海俊尓新材料有限公司 | Stress whitening resisting modified polypropylene material as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 彭鹤松等: "超细滑石粉填充改性ABS的性能研究", 《工程塑料应用》 * |
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Application publication date: 20170524 |