CN107974075A - Nylon 6 material that a kind of proof stress turns white and preparation method thereof - Google Patents
Nylon 6 material that a kind of proof stress turns white and preparation method thereof Download PDFInfo
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- CN107974075A CN107974075A CN201611201401.9A CN201611201401A CN107974075A CN 107974075 A CN107974075 A CN 107974075A CN 201611201401 A CN201611201401 A CN 201611201401A CN 107974075 A CN107974075 A CN 107974075A
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- nylon
- parts
- proof stress
- turns white
- stress turns
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
Abstract
The invention discloses the nylon 6 material that a kind of proof stress turns white, which is prepared by weight by following components：680~98 parts of nylon, 2~20 parts of high density polyethylene (HDPE), 5 30 parts of glass fibre, 2 ~ 10 parts of Research of Grafting Malaic Anhydride Onto Polyethylene, 0.1~1 part of optothermal stabilizer, 0.1~1 part of lubricant.The mechanical property of material prepared of the present invention is preferable, there is easy processing shaping, the proof stress blushing of especially material is controlled, the product occasions such as appearance are repeatedly being kept in the case of by external force available for shaping various requirement material, and available for a variety of colors and the product scope of other modification purposes.The high density polyethylene (HDPE) that the present invention selects activity higher carrys out modification of nylon 6, since it is easily combined into " island structure " with nylon 6 resin, a large amount of small crackles that resin is generated when being subject to external force to act on can be absorbed, prevent the further development of crackle, and then can slow down or prevent the stress whitening phenomenon of nylon 6 material.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to the nylon 6 material and its system that a kind of proof stress turns white
Preparation Method.
Background technology
Nylon 6 material is a kind of extremely common high molecular material at present, its application range is very extensive, but its product exists
It is stretched, bends during use, impacts the phenomenon that White Patches often occur when external force acts on, that is, our institutes
The stress whitening said.Product not only influences its appearance after stress whitening phenomenon occurs, and can cause product elongation at break
Reduction, intensity decreases and stress crack resistance performance are deteriorated, so as to seriously affect product use.At present for nylon 6 material system
Relatively conventional in the stress whitening solution of product is to be heat-treated product, i.e., product is placed in certain temperature conditionss
Under post-processed to eliminate its internal stress.But this method for product this body structure it is more complicated when, then internal stress eliminates effect
Fruit is just relatively more general, does not reach and solves the problems, such as its stress whitening.
The content of the invention
The present invention be directed to provide nylon 6 material and its preparation side that a kind of proof stress turns white the defects of the prior art
Method.The material has the characteristics that function admirable, machine-shaping are good, available for the occasion for being often subject to external force, can effectively reduce with
And the generation of stress whitening phenomenon is avoided, expand the application field of nylon 6 material material.
To achieve the above object, the technical solution adopted by the present invention is as follows：
The nylon 6 material that a kind of proof stress turns white, the material are prepared by weight by following components：
Melt index of the nylon 6 under the conditions of 230 DEG C/2.16Kg is 10~20g/10min；It is described polycthylene grafted
Melt index of the maleic anhydride under the conditions of 230 DEG C/2.16Kg is 5~10g/10min.
High density polyethylene (HDPE) melt index under the conditions of 220 DEG C/10Kg is 5-15g/10min.
The 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.
The monothioester type thermal stabilizing agent is selected from thio-2 acid double (lauryl alcohol) ester, thio-2 acids two (octadecyl alcolol)
Ester, (tridecanol) ester of thio-2 acid two or thio-2 acid two (tetradecyl alchohol) ester；
The organic tin heat stabilizer is selected from pink salt containing mercaptan, maleic acid pink salt or pant tin carboxylate；
The hindered amine is selected from naphthylamines, diphenylamines or p-phenylenediamine；
The hindered phenol is selected from 2,6- three-level butyl -4- methylphenols, double (3,5- three-level butyl -4- hydroxy phenyls) sulphur
Ether or four (β-(3,5- three-level butyl -4- hydroxy phenyls) propionic acid) pentaerythritol esters, β-(3,5- di-tert-butyl-hydroxy phenyl)
The positive octadecanol ester of propionic acid) (antioxidant 1076).
The preferred dimercapto 2-ethyl hexyl ethanoate dioctyltin (DOTTG) of the pink salt containing mercaptan or dimethyl dimercapto second
The different monooctyl ester tin of acid；
The maleic acid pink salt is selected from maleic acid di-n-butyl tin (DBTM)；
The pant tin carboxylate is selected from di-n-butyltin dilaurate (DBTL) or Bis(lauroyloxy)dioctyltin (DOTL).
The lubricant is selected from solid paraffin, atoleine, stearic amide, methylene bis stearic amide, N, N- second
Support double at least one of stearic amides or silicone oil.
The diphenyl phosphite such as (three [2.4- di-tert-butyl-phenyls] phosphite esters (irgasfos 168).
Another goal of the invention of the present invention is to provide the preparation method for the nylon 6 material that above-mentioned proof stress turns white, including
Following steps：
(1) by 80~98 parts of nylon 6,2-10 parts of Research of Grafting Malaic Anhydride Onto Polyethylene, 2-20 parts of high density polyethylene (HDPE)s, 5-30 parts
Glass fibre, 0.1~1 part of optothermal stabilizer and 0.1~1 part of lubricant are uniformly mixed；
(2) mixed material is added into extruding pelletization in double screw extruder, obtains modified nylon-6 material；The twin-screw squeezes
Go out machine extruder temperature for 200~240 DEG C；Screw speed is in 100~500r/min.
Screw speed is 400~500r/min in the step (2).
The present invention compared with the existing technology, has the advantages that：
1st, the present invention using twin screw extrusion process prepares modified nylon-6 material, has that flow is simple, continuous, production is imitated
The advantages of rate is high, product quality is stablized.
2nd, the mechanical property of material prepared of 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 appearance are repeatedly being kept in the case of by external force available for shaping various requirement material
Close, and available for a variety of colors and the product scope of other modification purposes.
3rd, due to adding glass fibre, so that the mechanical strength of modified nylon-6 material be significantly increased.
4th, the present invention selects high density polyethylene (HDPE), Research of Grafting Malaic Anhydride Onto Polyethylene to carry out modification of nylon 6, can absorb resin by
The a large amount of small crackles produced when being acted on to external force, prevent the further development of crackle, and then can slow down or prevent
The stress whitening phenomenon of nylon 6 material.
5th, the present invention selects 6 collective effect of Research of Grafting Malaic Anhydride Onto Polyethylene, high density polyethylene (HDPE) and nylon, have adjusted polymerization
Viscosity during thing melting extrusion, the problems such as uneven melting that runs into during extrusion, broken strip can be solved.
Embodiment
The present invention is further illustrated with reference to embodiments.
The quantitative measurement standard for the nylon 6 material that proof stress prepared by the present invention turns white is shown in Table 1.
Table 1
| Physical property | Test method |
| 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 pound onto plastics square plate, see the apparent state of blush of model；
Stress crack resistance performance test method：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 cracked with
State.
The extruder temperature of double screw extruder selected by example below is 200~240 DEG C；Screw speed for 100~
500r/min。
Embodiment 1
(1) by 85 parts of nylon, 6,15 parts of high density polyethylene (HDPE)s, 5 parts of glass fibres, 2 parts of Research of Grafting Malaic Anhydride Onto Polyethylene, 0.3
Part optothermal stabilizer (antioxidant 1076：Irgasfos 168=1：2, mass ratio) and 0.1 part of lubricant stearic acid acid amides through high-speed stirring
Mix uniformly mixed；
(2) said mixture is sent into extruding pelletization in double screw extruder, obtains modified nylon-6 material；
Double-screw extruder screw rotating speed is 400r/min in the step (2).
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 nylon, 6,2 parts of high density polyethylene (HDPE)s, 10 parts of glass fibres, 5 parts of Research of Grafting Malaic Anhydride Onto Polyethylene, 0.6
Part optothermal stabilizer (anti-oxidant DLTP：Antioxidant DBTL=1：1, mass ratio) and 0.5 part of lubricant silicone oil mixed through high-speed stirred
Close uniform；
(2) said mixture is sent into extruding pelletization in double screw extruder, obtains modified nylon-6 material；
Double-screw extruder screw rotating speed is 500r/min in the step (2).
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 nylon 6 resins, 10 parts of high density polyethylene (HDPE)s, 30 parts of glass fibres, 10 parts of polycthylene grafted maleic acids
Acid anhydride, 0.1 part of optothermal stabilizer (DLTP：2,6- three-level butyl -4- methylphenol=2：1, mass ratio) and 1 part of lubricant N, N- second
The double stearic amides of support are uniformly mixed through high-speed stirred；
(2) said mixture is sent into extruding pelletization in double screw extruder, obtains modified nylon-6 material；
Double-screw extruder screw rotating speed is 300r/min in the step (2).
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 nylon 6 resins, 5 parts of high density polyethylene (HDPE)s, 15 parts of glass fibres, 2 parts of polycthylene grafted maleic acids
Acid anhydride, 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 uniformly mixed through high-speed stirred；
(2) said mixture is sent into extruding pelletization in double screw extruder, obtains modified nylon-6 material；
Double-screw extruder screw rotating speed is 200r/min in the step (2).
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 nylon 6 resins, 20 parts of high density polyethylene (HDPE)s, 10 parts of glass fibres, 2 parts of polycthylene grafted maleic acids
Acid anhydride, 1 part of optothermal stabilizer (DOTL：DOTTG=1：2, mass ratio) and 0.6 part of lubricant silicone oil be uniformly mixed through high-speed stirred；
(2) said mixture is sent into extruding pelletization in double screw extruder, obtains modified nylon-6 material；
Double-screw extruder screw rotating speed is 100r/min in the step (2).
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
Nylon 6 resin is directly molded into the standard batten of test, the performance test results such as institute of table 2 by standard size
Show.
Table 2
As can be seen from Table 2, the mechanical strength for the nylon 6 material that the proof stress that prepared by 1-5 of the embodiment of the present invention turns white is bright
The aobvious mechanical strength higher than existing unmodified nylon 6 resin；And the stress-whitening resistance energy of material can be significantly improved,
Do not crack in 30S-1.5min, it is 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, those skilled in the art disclose according to the present invention, and not departing from improvement that scope made and modification all should be
Within protection scope of the present invention.
Claims (8)
1. the nylon 6 material that a kind of proof stress turns white, which is prepared by weight by following components：
6 80~98 parts of nylon,
2~20 parts of high density polyethylene (HDPE),
5-30 parts of glass fibre,
2 ~ 10 parts of Research of Grafting Malaic Anhydride Onto Polyethylene,
0.1~1 part of optothermal stabilizer,
0.1~1 part of lubricant.
2. the nylon 6 material that proof stress turns white according to claim 1, it is characterised in that the nylon 6 230 DEG C/
Melt index under the conditions of 2.16Kg is 10 ~ 20 g/10min；The Research of Grafting Malaic Anhydride Onto Polyethylene is in 230 DEG C/2.16Kg
Under the conditions of melt index be 5 ~ 10 g/10min.
3. the nylon 6 material that proof stress turns white according to claim 1, it is characterised in that the high density polyethylene (HDPE) is 220
DEG C/10Kg under the conditions of melt index be 5-15g/10min.
4. the nylon 6 material that proof stress turns white according to claim 1, it is characterised in that the optothermal stabilizer is selected from
In monothioester type thermal stabilizing agent, organic tin heat stabilizer, hindered amine, hindered phenol, diphenyl phosphite and triphenyl phosphite
One or more.
5. the nylon 6 material that proof stress turns white according to claim 4, it is characterised in that the thio esters thermostabilization
It is double that 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.
6. the nylon 6 material that proof stress turns white according to claim 1, it is characterised in that the lubricant is selected from solid
Paraffin, atoleine, stearic amide, methylene bis stearic amide, N, in N- ethylene bis stearic acid amides and silicone oil at least
It is a kind of.
7. preparing the method for the nylon 6 material that any one of the claim 1-6 proof stress turns white, comprise the following steps：
（1）By 80~98 parts of nylon 6,2-10 parts of Research of Grafting Malaic Anhydride Onto Polyethylene, 2-20 parts of high density polyethylene (HDPE)s, 5-30 parts of glass
Fiber, 0.1~1 part of optothermal stabilizer and 0.1~1 part of lubricant are uniformly mixed；
（2）Mixed material is added into extruding pelletization in double screw extruder, obtains modified nylon-6 material；The double screw extruder
Extruder temperature is 200~240 DEG C；Screw speed is in 100~500 r/min.
8. the preparation method for the nylon 6 material that proof stress turns white according to claim 7, it is characterised in that the step（2）
Middle screw speed is 400~500 r/min.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2016109217215 | 2016-10-21 | ||
| CN201610921721 | 2016-10-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107974075A true CN107974075A (en) | 2018-05-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611201401.9A Withdrawn CN107974075A (en) | 2016-10-21 | 2016-12-22 | Nylon 6 material that a kind of proof stress turns white and preparation method thereof |
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| Country | Link |
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| CN (1) | CN107974075A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665848A (en) * | 2013-11-28 | 2014-03-26 | 方万漂 | Polyethylene and nylon 6 blending modified barrier material |
| CN103897267A (en) * | 2014-02-26 | 2014-07-02 | 上海金发科技发展有限公司 | Nylon modified stress resistance whitening polypropylene compound and preparation method thereof |
-
2016
- 2016-12-22 CN CN201611201401.9A patent/CN107974075A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665848A (en) * | 2013-11-28 | 2014-03-26 | 方万漂 | Polyethylene and nylon 6 blending modified barrier material |
| CN103897267A (en) * | 2014-02-26 | 2014-07-02 | 上海金发科技发展有限公司 | Nylon modified stress resistance whitening polypropylene compound and preparation method thereof |
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