CN102492076A - Compatilizer, preparation method thereof and engineering plastics using compatiblizer - Google Patents
Compatilizer, preparation method thereof and engineering plastics using compatiblizer Download PDFInfo
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- CN102492076A CN102492076A CN2011103988368A CN201110398836A CN102492076A CN 102492076 A CN102492076 A CN 102492076A CN 2011103988368 A CN2011103988368 A CN 2011103988368A CN 201110398836 A CN201110398836 A CN 201110398836A CN 102492076 A CN102492076 A CN 102492076A
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Abstract
The invention discloses a compatilizer, a preparation method thereof and engineering plastics using the compatilizer. The compatilizer is a terpolymer, namely glycidyl methacrylate-styrene-acrylonitrile (GMA-St-AN) polymerized by glycidyl methacrylate, styrene and acrylonitrile. The engineering plastics are made of 70 mass parts of polyamide 6 (PA6) and 30 mass parts of acrylonitrile-butadiene-styrene (ABS), and 1 to 5 mass parts of GMA-St-AN is added. Compared with the traditional styrene-maleic anhydride (SMA) and acrylonitrile-butadiene-styrene-grafted-maleic anhydride (ABS-g-MAH), the compatilizer has a better effect when applied to PA6/ABS alloys.
Description
Technical field
The present invention relates to polymeric material field, the engineering plastics of particularly a kind of compatilizer and preparation method and this compatilizer of use.
Background technology
Flourish along with automobile, electronics, electric, communication, mechanical industry, macromolecular material more and more receives people's favor.But also be difficult to satisfy the demand of practical application at a lot of simple resin modifieds of occasion, the polyblend technology can be effectively the comprehensive property of each resin, the handling ease of system, the material of excellent performance.And compatilizer is the homophase resin gordian technique of making alloy not, and compatilizer can reduce surface tension, promotes the dispersion of phase, and the couplet that stops disperse phase also; Interfacial thickness is increased, increase alternate bounding force, improve thermostability; Refinement disperse phase particle diameter forms the stable morphology structure, broadening engineering resin process window.
Compatilizer is claimed expanding material again, is meant by means of intermolecular linkage force, impels inconsistent two kinds of polymer scales to be combined in one, and then obtains the auxiliary agent of stable blend, is meant polymer bulking agents here.PE-g-ST, PP-g-ST, ABS-g-MAH, PE-g-MAH, PP-g-MAH etc. are applied in the modifying plastics, obtain the good blend property material of performance.
Use at present more compatilizer usually with
Maleic anhydrideGrafting, relatively polarity is more intense with other monomer for maleic anhydride monomer, and compatible effect is relatively good.The maleic anhydride graft compatilizer makes material have high polarity and reactivity through introducing strong polar reaction property group, is a kind of macromolecule interfacial
Coupling agent, compatilizer, dispersion promotor.Be mainly used in halogen-free flameproof, filling, glass strengthen, toughness reinforcing, metal bonding, alloy are compatible etc., can improve the consistency of matrix material and the dispersiveness of filler greatly, thereby improve the mechanical intensity of matrix material.The maleic anhydride graft compatilizer can improve mineral filler and organic resin consistency, improves stretching, the shock strength of product, realizes high the filling, reduces resin demand, improves the processing rheological, improves surface smoothness.
But
Maleic anhydrideIt is undesirable to be grafted in the PA6/ABS alloy result of use.
Summary of the invention
The present invention is for overcoming at present
Maleic anhydrideIt is undesirable to be grafted in the PA6/ABS alloy result of use, and a kind of compatilizer is provided, and the preparation method of this compatilizer and method of use.
The present invention for realizing the technical scheme that its purpose adopts is: a kind of compatilizer, described compatilizer are to be the terpolymer GMA-St-AN that principal monomer is polymerized by SY-Monomer G, vinylbenzene, vinyl cyanide; The raw material composition and the respective quality mark ratio thereof that prepare this compatilizer are:
Vinylbenzene (St) 15-25;
SY-Monomer G 10-20;
Vinyl cyanide 10-20;
Diisopropyl azodicarboxylate 3-8;
X 2073 1-5;
T-lauryl mercaptan 1-5;
Active calcium phosphate 5-15;
De-salted water 20-40.
Further, in above-mentioned a kind of compatilizer, the raw material composition and the respective quality ratio thereof that prepare this compatilizer are:
Vinylbenzene (St) 20;
SY-Monomer G 15;
Vinyl cyanide 15;
Diisopropyl azodicarboxylate 5;
X 2073 3;
T-lauryl mercaptan 3;
Active calcium phosphate 9;
De-salted water 30.
Further, in above-mentioned a kind of compatilizer: described vinylbenzene (St) is the polymerization-grade vinylbenzene (St) of commercially available purity >=99.5%.
The present invention also provides the preparation method of the compatilizer of the above, may further comprise the steps:
Step 1, the raw material that will prepare this compatilizer add the water dispersion system in the 3L three-necked bottle in the ratio of top respective quality, and spherical condenser lead to water of condensation, starts to stir also to control rotating speed about 80rpm/hr, keeps constant;
Step 2, in 40～90min, temperature is risen to 65～75 ℃, the beginning polyreaction;
Step 3, to keep stirring velocity between the reaction period constant in the 80rpm/hr left and right sides.
The monomer overwhelming majority consumes behind step 4, the reaction 3hr, and can suitably rise to temperature about 80 ℃ this moment;
After 4.5～6.0hr is carried out in step 5, reaction, temperature is elevated to more than 90 ℃;
Step 6, maturation reaction: control is reflected at more than 90 ℃ keeps 30～60min.
Step 7, remove well heater, begin to cool down.Can obtain faint yellow heavy-gravity compatilizer GMA-St-AN this moment.
The invention provides the engineering plastics of a kind of GMA-St-AN of use as compatilizer, the mass ratio of described engineering plastics consists of:
PA6 70；
ABS 30；
The mass percent that accounts at the compatilizer described in the whole engineering plastics is 1～8%.
Further, in the above-mentioned engineering plastics: the mass percent that accounts at the compatilizer described in the whole engineering plastics is 3%～4%.
Further, in the above-mentioned engineering plastics: described PA6 is a polycaprolactam.
Further, in the above-mentioned engineering plastics: described ABS is that mass ratio 20-30% propylene is fine, 40-70% divinyl, 20～30% styrene triblock copolymers
Further, in above-mentioned a kind of compatilizer: described vinylbenzene (St) is the polymerization-grade vinylbenzene (St) of commercially available purity >=99.5%.
In the PA6/ABS alloy, use, GMA-St-AN of the present invention makes compatilizer and compares and traditional SMA and ABS-g-MAH better effects if.
Embodiment
Press routine mass component ratio and prepare raw material:
Vinylbenzene (St) 20;
SY-Monomer G 15;
Vinyl cyanide 15;
Diisopropyl azodicarboxylate 5;
X 2073 3;
T-lauryl mercaptan 3;
Active calcium phosphate 9;
De-salted water 30.
Above-mentioned raw material is put into the water dispersion system in the 3L three-necked bottle, and spherical condenser leads to water of condensation, starts to stir and control rotating speed about 80rpm/hr, keeps constant; Three liters of three-necked bottles that present embodiment uses are commercially available three-necked bottle, and this three-necked bottle intermediary neck inserts whisking appliance, and a side is inserted TM, an other side through a threeway respectively with opening for feed and spherical cold doubtful device.
Step 2, in 40～90min, temperature is risen to 65～75 ℃, the beginning polyreaction.
Step 3, to keep stirring velocity between the reaction period constant in the 80rpm/hr left and right sides.
The monomer overwhelming majority consumes behind step 4, the reaction 3hr, and can suitably rise to temperature about 80 ℃ this moment.
After 4.5～6.0hr is carried out in step 5, reaction, temperature is elevated to more than 90 ℃.
Step 6, maturation reaction: control is reflected at more than 90 ℃ keeps 30～60min.
Step 7, remove well heater, begin to cool down.Can obtain faint yellow heavy-gravity compatilizer GMA-St-AN this moment.
Among this preparation method, be to utilize the method for heating in water bath temperature control to carry out temperature controlled.
With the ABS of 30 parts of quality and the PA6 of 70 parts of quality, do not add any compatilizer and process engineering plastics 1#PA6/ABS (7/3).
With the ABS of 30 parts of quality and the PA6 of 70 parts of quality, the GMA-St-AN that adds 3 parts of quality processes 2# engineering plastics PA6/ABS (7/3).
With the ABS of 30 parts of quality and the PA6 of 70 parts of quality, the GMA-St-AN that adds 5 parts of quality processes 3# engineering plastics PA6/ABS (7/3).
Table 1
Top ASTM D-638 etc. is the testing method of American Society Testing and Materials for this rerum natura.
Table 2 is: with the ABS of 30 parts of quality and the PA6 of 70 parts of quality, do not add any compatilizer and process engineering plastics 1#PA6/ABS (7/3).
With the ABS of 30 parts of quality and the PA6 of 70 parts of quality, the SMA that adds 3 parts of quality processes 2# engineering plastics PA6/ABS (7/3).
With the ABS of 30 parts of quality and the PA6 of 70 parts of quality, the SMA that adds 5 parts of quality processes 3# engineering plastics PA6/ABS (7/3).
Table 2
Top ASTM D-638 etc. is the testing method of American Society Testing and Materials for this rerum natura.
Table 3 is the PA6 with the ABS of 30 parts of quality and 70 parts of quality, does not add any compatilizer and processes 1#PA6/ABS (7/3).
With the ABS of 30 parts of quality and the PA6 of 70 parts of quality, the ABS-g-MAH that adds 3 parts of quality processes 2# engineering plastics PA6/ABS (7/3).
With the ABS of 30 parts of quality and the PA6 of 70 parts of quality, the ABS-g-MAH that adds 5 parts of quality processes 3# engineering plastics PA6/ABS (7/3).
Table 3
By above-mentioned table 1, table 2, table 3 contrast can learn compatilizer of the present invention (SY-Monomer G, vinylbenzene, the fine GMA-St-AN of propylene) in the PA/ABS alloy effect all more obvious than phenylethylene-maleic anhydride and ABS grafted maleic anhydride effect: consistency is good; Toughness promotes obviously; Strength retention is high, and the section effect does not have the layering skin effect phenomenon.This compatilizer also can be used for polyblend fields such as PC/ABS, ABS/PET, ABS/PBT.
Claims (9)
1. compatilizer is characterized in that: described compatilizer is to be the terpolymer (GMA-St-AN) that principal monomer is polymerized by SY-Monomer G, vinylbenzene, vinyl cyanide; The raw material composition and the respective quality mark ratio thereof that prepare this compatilizer are:
Vinylbenzene (St) 15-25;
SY-Monomer G 10-20;
Vinyl cyanide 10-20;
Diisopropyl azodicarboxylate 3-8;
X 2073 1-5;
T-lauryl mercaptan 1-5;
Active calcium phosphate 5-15;
De-salted water 20-40.
2. a kind of compatilizer according to claim 1 is characterized in that, the raw material composition and the respective quality ratio thereof that prepare this compatilizer are:
Vinylbenzene (St) 20;
SY-Monomer G 15;
Vinyl cyanide 15;
Diisopropyl azodicarboxylate 5;
X 2073 3;
T-lauryl mercaptan 3;
Active calcium phosphate 9;
De-salted water 30.
3. a kind of compatilizer according to claim 1 and 2 is characterized in that: described vinylbenzene (St) is the polymerization-grade vinylbenzene (St) of commercially available purity >=99.5%.
4. preparation method according to claim 1 or 2 described compatilizers is characterized in that: may further comprise the steps:
Step 1, the raw material that will prepare this compatilizer add the water dispersion system in the 3L three-necked bottle in the ratio of top respective quality, and spherical condenser lead to water of condensation, starts to stir also to control rotating speed about 80rpm/hr, keeps constant;
Step 2, in 40～90min, temperature is risen to 65～75 ℃, the beginning polyreaction;
Step 3, to keep stirring velocity between the reaction period constant in the 80rpm/hr left and right sides;
The monomer overwhelming majority consumes behind step 4, the reaction 3hr, and can suitably rise to temperature about 80 ℃ this moment;
After 4.5～6.0hr is carried out in step 5, reaction, temperature is elevated to more than 90 ℃;
Step 6, maturation reaction: control is reflected at more than 90 ℃ keeps 30～60min;
Step 7, remove well heater, begin to cool down.Can obtain faint yellow heavy-gravity compatilizer GMA-St-AN this moment.
5. according to the preparation method of claim 4, it is characterized in that: temperature control is to adopt the method for heating in water bath temperature control to carry out.
6. engineering plastics that use the described compatilizer of claim 1, it is characterized in that: the mass ratio of described engineering plastics consists of:
PA6 70；
ABS 30；
The mass percent that accounts at the compatilizer described in the whole engineering plastics is 1～8%.
7. engineering plastics according to claim 6 is characterized in that: the mass percent that accounts at the compatilizer described in the whole engineering plastics is 3%～4%.
8. according to right 6 described engineering plastics, it is characterized in that: described PA6 is a polycaprolactam.
9. according to right 6 described engineering plastics, it is characterized in that: described ABS is that mass ratio 20-30% propylene is fine, 40-70% divinyl, 20～30% styrene triblock copolymers.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104877326A (en) * | 2015-05-14 | 2015-09-02 | 上海日之升新技术发展有限公司 | Special compatilizer for improving hydrolysis heat stability of PC/ABS (polycarbonate/acrylonitrile-butadiene-styrene) alloy and alloy |
| CN106084614A (en) * | 2016-06-20 | 2016-11-09 | 吕智 | Prevent the preparation method of the compatilizer of PBT alloy material warp and prepared compatilizer thereof |
| CN107189414A (en) * | 2017-06-20 | 2017-09-22 | 苏州旭光聚合物有限公司 | Long glass fiber reinforced modification of nylon |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104877326A (en) * | 2015-05-14 | 2015-09-02 | 上海日之升新技术发展有限公司 | Special compatilizer for improving hydrolysis heat stability of PC/ABS (polycarbonate/acrylonitrile-butadiene-styrene) alloy and alloy |
| CN104877326B (en) * | 2015-05-14 | 2017-01-18 | 上海日之升新技术发展有限公司 | Special compatilizer for improving hydrolysis heat stability of PC/ABS (polycarbonate/acrylonitrile-butadiene-styrene) alloy and alloy |
| CN106084614A (en) * | 2016-06-20 | 2016-11-09 | 吕智 | Prevent the preparation method of the compatilizer of PBT alloy material warp and prepared compatilizer thereof |
| CN107189414A (en) * | 2017-06-20 | 2017-09-22 | 苏州旭光聚合物有限公司 | Long glass fiber reinforced modification of nylon |
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Application publication date: 20120613 |