CN107541026A - PET resin that a kind of proof stress turns white and preparation method thereof - Google Patents
PET resin that a kind of proof stress turns white and preparation method thereof Download PDFInfo
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- CN107541026A CN107541026A CN201610510968.8A CN201610510968A CN107541026A CN 107541026 A CN107541026 A CN 107541026A CN 201610510968 A CN201610510968 A CN 201610510968A CN 107541026 A CN107541026 A CN 107541026A
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- pet resin
- proof stress
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Abstract
The present invention provides PET resin that a kind of proof stress turns white and preparation method thereof, its by PET resin, calcium carbonate superfine powder, glass fibre, methyl methacrylate, optothermal stabilizer lubricant, blended, extrusion is prepared.Present invention adds the methyl methacrylate of active functional group's graft and calcium carbonate superfine powder to be used in combination, improve its good bonding strength with resin matrix, network structure can be internally formed in resin simultaneously, so as to be produced by reduction defect and blushing after external force, so as to slow down or prevent the stress whitening phenomenon of PET resin.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to the PET resin and its preparation that a kind of proof stress turns white
Method.
Background technology
Polyethylene terephthalate (PET) resin is a kind of extremely conventional high polymer material at present, and it applies model
Enclose very extensive, but its product is stretched, bent, impact etc. when external force acts on and local hair often occurs in use
White phenomenon, that is, the stress whitening described in us.Product not only influences its outward appearance after stress whitening phenomenon occurs, and
The reduction of product elongation at break, intensity decreases and stress crack resistance performance can be caused to be deteriorated, have a strong impact on that product uses.At present
For it is relatively conventional in the stress white hair solution of PET resin product be to be heat-treated product, i.e., product is placed in
Post-processed under certain temperature conditionss to eliminate its internal stress.This method for product this body structure it is more complicated when, then
Internal stress eradicating efficacy is just relatively more general.
The content of the invention
The present invention be directed to the defects of prior art and a kind of caused proof stress turns white PET resin and preparation method thereof.
The material has the characteristics that function admirable, machine-shaping are good, and emphasis is that material preparation method is simple, production efficiency is high, while can
For being often subject to the occasion of external force, the generation of stress whitening phenomenon effectively can be reduced and avoided, has expanded PET resin material
Application field.
To achieve the above object, the technical solution adopted by the present invention is as follows：
The PET resin that a kind of proof stress turns white, the material are prepared by weight by following components：
The melt index of described PET resin is 10~20g/10min under the conditions of 230 DEG C/2.16kg.
The mesh number of the calcium carbonate superfine powder is 6000~7000 mesh.
The melt index of described methyl methacrylate is 5~10g/10min under the conditions of 230 DEG C/2.16kg.
Described optothermal stabilizer be selected from monothioester type thermal stabilizing agent, organic tin heat stabilizer, hindered amine, hindered phenol,
It is more than one or both of diphenyl phosphite or triphenyl phosphite.
Described monothioester type thermal stabilizing agent is selected from thio-2 acid double (lauryl alcohol) ester (DLTP), thio-2 acids two
(octadecyl alcolol) ester (DSTP), thio-2 acid two (tridecanol) ester (DTDTP) or thio-2 acid two (tetradecyl alchohol) ester (DMTP)
At least one of；
Described organic tin heat stabilizer in pink salt containing mercaptan, maleic acid pink salt or pant tin carboxylate at least one
Kind；
Described hindered amine is selected from least one of naphthylamines, diphenylamines or p-phenylenediamine；
Described hindered phenol is selected from 2,6- three-level butyl -4- methylphenols (BHT), double (3,5- three-level butyl -4- hydroxy benzenes
Base) thioether, β-positive octadecanol ester (antioxidant 1076) of (3,5- di-tert-butyl-hydroxy phenyl) propionic acid or four (β-(3,5- tri-
At least one of level butyl -4- hydroxy phenyls) propionic acid) pentaerythritol ester (antioxidant 1010).
The preferred dimercapto 2-ethyl hexyl ethanoate dioctyltin (DOTTG) of described pink salt containing mercaptan or dimethyl dimercapto second
The different monooctyl ester tin of acid；
Described maleic acid pink salt is selected from maleic acid di-n-butyl tin (DBTM)；
Described pant tin carboxylate is selected from di-n-butyltin dilaurate (DBTL) or Bis(lauroyloxy)dioctyltin (DOTL).
Described lubricant is selected from solid paraffin, atoleine, stearic amide (SR), methylene bis stearic amide, N,
At least one of N- ethylene bis stearic acid amides (EBS) or silicone oil.
Another goal of the invention of the present invention is to provide the preparation method of the PET resin that above-mentioned proof stress turns white, including with
Lower step：
(1) by 80~98 parts of PET resin, 2~20 parts of calcium carbonate superfine powder, 2~10 parts, 5~30 parts of methyl methacrylate
Glass fibre, 0.1~1 part of 0.1~1 part of optothermal stabilizer and lubricant are well mixed；
(2) mixed material is added into extruding pelletization in double screw extruder, obtains PET resin material；The twin-screw extrusion
Machine extruder temperature is 200~240 DEG C；Screw speed is in 100~500r/min.
Preferably, screw speed is 400~500r/min in the step (2).
Present invention adds methyl methacrylate, calcium carbonate superfine powder, their active functional group's grafts, with resin
The good bonding strength of matrix, while network structure can be internally formed in resin, so as to by reduction defect and hair after external force
Bai Xianxiang generation, its application field is then expanded.
The present invention compared with the existing technology, has the advantages that：
1st, the present invention prepares PET resin using twin screw extrusion process, with flow is simple, continuous, production efficiency is high, production
The advantages of quality is stable.
2nd, the mechanical property of material prepared by the present invention is preferable, has the characteristics that easy processing shaping, especially material is resistance to
Stress whitening phenomenon is controlled, and the product fields such as outward appearance are repeatedly being kept in the case of by external force available for shaping various requirement material
Close.
3rd, proof stress prepared by the present invention turns white PET resin available for a variety of colors and products neck of other modification purposes
Domain.
4th, the present invention select calcium carbonate superfine powder, higher " island structure ", energy can be easily combined into PET resin because it is active
Absorb resin and produce crazing when being acted on by external force and caused a large amount of small crackles, prevent the further development of crackle,
And then it can slow down or prevent the stress whitening phenomenon of PET resin.
5th, the present invention selects methyl methacrylate, calcium carbonate superfine powder and PET collective effects, have adjusted polymer melting and squeezes
Viscosity when going out, the problems such as can solve the problem that the uneven melting run into during extrusion, broken strip.
Embodiment
The present invention is further illustrated with reference to embodiments.
The quantitative measurement standard for the PET resin that proof stress prepared by the present invention turns white is shown in Table 1.
Table 1
| Physical property | Method of testing |
| Tensile strength | ASTM D638 |
| Bending strength | ASTM D790 |
| Bending modulus | ASTM D790 |
| Izod notch impact strengths (izodtest) | ASTM D256 |
| Izod unnotched impact strengths (izodtest) | ASTM D256 |
| Density | ASTM D792 |
| Proof stress turns white performance | Company standard |
| Stress crack resistance performance | Company standard |
Wherein, proof stress turns white performance test methods：It is the plastic square that size is 250mm*200mm*2mm by material injection
Plate, 500g steel balls fall from 1 meter of height and pounded 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, it is curved with fixed angle
Folding, and fixes its both ends, and glacial acetic acid or acetone are smeared in its stress raiser, observe by solvent etched to the time ftractureed with
State.
Embodiment 1
(1) by 85 parts of PET resins, 15 parts of calcium carbonate superfine powders (6000 mesh), 5 parts of glass fibres, 2 parts of methyl methacrylates
Ester, 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) said mixture is sent into extruding pelletization in double screw extruder, obtains PET resin；
Double-screw extruder screw temperature is 210 DEG C in described step (2), screw speed 400r/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 PET, 2 parts of calcium carbonate superfine powders (7000 mesh), 10 parts of glass fibres, 5 parts of methyl methacrylates, 0.6
Part optothermal stabilizer (DLTP：DBTL=1：1, mass ratio) and 0.5 part of lubricant silicone oil be well mixed through high-speed stirred；
(2) said mixture is sent into extruding pelletization in double screw extruder, obtains PET resin；
Double-screw extruder screw temperature is 230 DEG C in described step (2), screw speed 500r/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 PET resins, 10 parts of calcium carbonate superfine powders (7000 mesh), 30 parts of glass fibres, 10 parts of methyl methacrylates
Ester, 0.1 part of optothermal stabilizer (DLTP：BHT=2：1, mass ratio) and 1 part of Lubricate EBS be well mixed through high-speed stirred；
(2) said mixture is sent into extruding pelletization in double screw extruder, obtains PET resin；
Double-screw extruder screw temperature is 200 DEG C in described step (2), screw speed 300r/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 PET resins, 5 parts of calcium carbonate superfine powders (7000 mesh), 15 parts of glass fibres, 2 parts of methyl methacrylates
Ester, 0.6 part of optothermal stabilizer (DBTL：DBTM=1：1, mass ratio) and 0.5 part of lubricant solids paraffin and atoleine (quality
Than 1：1) it is well mixed through high-speed stirred；
(2) said mixture is sent into extruding pelletization in double screw extruder, obtains PET resin；
Double-screw extruder screw temperature is 240 DEG C in described step (2), screw speed 200r/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 PET resins, 20 parts of calcium carbonate superfine powders (7000 mesh), 10 parts of glass fibres, 2 parts of methyl methacrylates
Ester, 1 part of optothermal stabilizer (DOTL：DOTTG=1：2, mass ratio) and 0.6 part of lubricant silicone oil be well mixed through high-speed stirred；
(2) said mixture is sent into extruding pelletization in double screw extruder, obtains PET resin；
Double-screw extruder screw temperature is 200 DEG C in described step (2), screw speed 100r/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
PET resin is directly molded into the standard batten of test by standard size, the performance test results are as shown in table 2.
Table 2
As can be seen from Table 2, by the ratio between suitable control each component, material is made in contrast to existing PET resin
For material, performance is suitable in terms of the mechanical property of materials and density；But the stress-whitening resistance energy of material can be significantly improved,
It is set to be used in the multiple stress occasion required to mechanical property, appearance property etc..
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using this hair
It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to implementation here
Example, for those skilled in the art according to the announcement of the present invention, not departing from improvement that scope made and modification all should be
Within protection scope of the present invention.
Claims (9)
- A kind of 1. PET resin that proof stress turns white, it is characterised in that：It is prepared by weight by following components：80~98 parts of PET resin,2~20 parts of calcium carbonate superfine powder,5~30 parts of glass fibre,2 ~ 10 parts of methyl methacrylate,0.1~1 part of optothermal stabilizer,0.1~1 part of lubricant.
- 2. the PET resin that a kind of proof stress according to claim 1 turns white, it is characterised in that：Described PET resin melts It is 10 ~ 20g/10min under the conditions of 230 DEG C/2.16 kg to melt index.
- 3. the PET resin that a kind of proof stress according to claim 1 turns white, it is characterised in that：The calcium carbonate superfine powder Mesh number is 6000~7000 mesh.
- 4. the PET resin that a kind of proof stress according to claim 1 turns white, it is characterised in that：Described methacrylic acid The melt index of methyl esters is 5 ~ 10 g/10min under the conditions of 230 DEG C/2.16 kg.
- 5. the PET resin that a kind of proof stress according to claim 1 turns white, it is characterised in that：Described optothermal stabilizer Selected from monothioester type thermal stabilizing agent, organic tin heat stabilizer, hindered amine, hindered phenol, diphenyl phosphite or phosphorous triphenyl phosphate It is more than one or both of ester.
- 6. the PET resin that a kind of proof stress according to claim 5 turns white, it is characterised in that：Described thio esters heat It is double that stabilizer 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）At least one of ester；Described organic tin heat stabilizer is selected from least one of pink salt containing mercaptan, maleic acid pink salt or pant tin carboxylate；Described hindered amine is selected from least one of 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, β-（3,5- di-tert-butyl-hydroxy phenyls）The positive octadecanol ester of propionic acid or four (β-(3,5- three-level butyl -4- hydroxy phenyls) third At least one of acid) pentaerythritol ester.
- 7. the PET resin that a kind of proof stress according to claim 6 turns white, it is characterised in that：Described pink salt containing mercaptan It is preferred that dimercapto 2-ethyl hexyl ethanoate dioctyltin 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.
- 8. the PET 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, in N- ethylene bis stearic acid amides or silicone oil It is at least one.
- 9. the preparation method for the PET resin that a kind of proof stress as claimed in claim 1 turns white, it is characterised in that：Including following Step：（1）By 80~98 parts of PET resin, 2~20 parts of calcium carbonate superfine powder, 2~10 parts of methyl methacrylate, 5~30 parts of glass Fiber, 0.1~1 part of 0.1~1 part of optothermal stabilizer and lubricant are well mixed；（2）Mixed material is added into extruding pelletization in double screw extruder, obtains PET resin material；The double screw extruder spiral shell Bar temperature is 200~240 DEG C；Screw speed is in 100~500 r/min.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610510968.8A CN107541026A (en) | 2016-06-29 | 2016-06-29 | PET resin that a kind of proof stress turns white and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610510968.8A CN107541026A (en) | 2016-06-29 | 2016-06-29 | PET resin that a kind of proof stress turns white and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN107541026A true CN107541026A (en) | 2018-01-05 |
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| CN201610510968.8A Pending CN107541026A (en) | 2016-06-29 | 2016-06-29 | PET resin that a kind of proof stress turns white and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111715499A (en) * | 2020-06-16 | 2020-09-29 | 安徽博晟亿电力科技有限公司 | Anti-corrosion treatment method for pig iron casting for railway |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093673A (en) * | 2011-01-18 | 2011-06-15 | 南通市东方塑胶有限公司 | Polyester having thermal ageing resistant performance and production method thereof |
-
2016
- 2016-06-29 CN CN201610510968.8A patent/CN107541026A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093673A (en) * | 2011-01-18 | 2011-06-15 | 南通市东方塑胶有限公司 | Polyester having thermal ageing resistant performance and production method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111715499A (en) * | 2020-06-16 | 2020-09-29 | 安徽博晟亿电力科技有限公司 | Anti-corrosion treatment method for pig iron casting for railway |
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