CN103146176B - Modification compatibilizer of PPO/PA (Poly-p-phenylene oxide/polyacrylate) alloy and PPO/PA alloy - Google Patents
Modification compatibilizer of PPO/PA (Poly-p-phenylene oxide/polyacrylate) alloy and PPO/PA alloy Download PDFInfo
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- CN103146176B CN103146176B CN201310102133.5A CN201310102133A CN103146176B CN 103146176 B CN103146176 B CN 103146176B CN 201310102133 A CN201310102133 A CN 201310102133A CN 103146176 B CN103146176 B CN 103146176B
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Abstract
The invention relates to a modification compatibilizer of PPO/PA (Poly-p-phenylene oxide/polyacrylate) alloy and a PPO/PA alloy. The compatibilizer is characterized by being a grafted copolymer of polyphenyl ether, glycidyl methacrylate and styrene; and the PPO/PA alloy with the compatibilizer is characterized by comprising the following components in percentage by weight: 50-59.5% of polyphenyl ether, 31.5-40.4% of nylon, 0.1-18% of the compatibilizer and 0.1-0.5% of antioxidant. Compared with the prior art, the prescription of the compatibilizer matching with the PPO/PA disclosed by the invention can be used for greatly improving the compatibility of the PPO/PA alloy and improving the mechanical property and water resisting property of the PPO/PA alloy and is in good condition of industrial application.
Description
Technical field
The present invention relates to polymer alloy field, specifically refer to a kind of PPO/PA alloy modification expanding material and PPO/PA alloy.
Background technology
As the Typical Representative of engineering plastic alloy, PPO/PA alloy combines polyphenylene oxide (PPO) and nylon (PA) bi-material advantage separately, by the complementation in each component performance, obtaining the PPO/PA alloy material that over-all properties is better than any single component, is very important a kind of premium quality product in modified polyphenylene oxide alloy.PPO/PA alloy is widely used in the industries such as automobile, machinery, electric, office equipment with advantages such as its excellent mechanical property, resistance toheat, dimensional stability and processing fluidities.
Polyphenylene oxide is nonpolar amorphous polymer, and nylon is the crystalline polymer of polarity, and the two simple blend must be caused two-phase laminated flow, and interfacial adhesion is poor, and affect the improvement of its performance, material does not have practical value.Therefore, be solve the compatibility problem between component by the gordian technique of polyphenylene oxide and nylon alloy.Conventional method in system, adds suitable expanding material to improve the consistency of blend.Therefore, the exploitation of highly effective reaction expanding material is the core of preparation high-performance PPO/PA alloy material.
The domestic research and development to PPO/PA alloy system expanding material mainly concentrate on and adopt maleic anhydride to carry out Reaction extrusion grafting.But, because the melt fluidity of polyphenylene oxide own is poor, the temperature general requirement of carrying out melt blending reactive extrursion is very high, far exceedes the boiling point of maleic anhydride monomer, its molecular chain lacks again the higher grafting site of reactive behavior, there is larger difficulty in this technique in industrial practical application.
Summary of the invention
Technical problem to be solved by this invention provides a kind of for the present situation of prior art can effectively improve PPO and PA consistency and be easy to the PPO/PA alloy modification expanding material of industrial application.
Another technical problem to be solved by this invention is to provide a kind of PPO/PA alloy using above-mentioned modification expanding material.
Another technical problem to be solved by this invention is to provide a kind of preparation method of PPO/PA alloy.
The present invention solves the problems of the technologies described above adopted technical scheme: this PPO/PA alloy modification expanding material, it is characterized in that this expanding material is polyphenylene oxide, glycidyl methacrylate and cinnamic graft copolymer, the preparation method of this graft copolymer is as follows:
(1) glycidyl methacrylate and vinylbenzene are configured to grafted monomer mixed solution according to weight ratio 1:1, then the initiator accounting for grafted monomer mixed solution total amount 4 ~ 6% is joined in mixed solution dissolve, obtain grafting mixed solution;
(2) polyphenylene oxide and described grafting mixed solution are fully mixed 5 ~ 10min, obtain total mixed solution; Wherein grafting mixed solution accounts for 6 ~ 10% of total mixed solution weight;
(3) joined in torque rheometer by described total mixed solution carry out melting graft reaction at 50-70rpm, 220-250 DEG C, the reaction times is 6-10min;
(4) reaction terminate after by material cooled, then with pulverizer pulverize, namely obtain granular PPO/PA alloy modification expanding material.
Above-mentioned initiator is preferably dicumyl peroxide.
Use the PPO/PA alloy of above-mentioned expanding material, it is characterized in that comprising following weight composition:
Polyphenylene oxide 50-59.5%
Nylon 31.5-40.4%
Expanding material 0.1-18%
Oxidation inhibitor 0.1-0.5%
Described oxidation inhibitor is polyphenol antioxidant 1010.
Polyphenylene oxide in such scheme can use of the prior art any one, preferred described polyphenylene oxide is by 2, the nonpolar linear polymer that 6-xylenol carries out oxidative dimerization with oxygen and obtains under the effect of copper-ammonium catalyzer contains in molecular backbone chain
the thermoplastic engineering plastic of chain link.
Described nylon is nylon 6.
The preparation method of above-mentioned PPO/PA alloy, is characterized in that comprising the steps:
The dry 12-24h at 80 ~ 90 DEG C by polyphenylene oxide and nylon, then after polyphenylene oxide, nylon and alloy modification expanding material being stirred 5-10min in agitator, join in torque rheometer 230-250 DEG C, rotating speed carries out melt blending under being 50-70rpm, reaction times is 10-15min, can obtain the block PPO/PA alloy material of functional polyphenylene ether graft copolymer capacity increasing modifying.
Compared with prior art, melting graft reaction is there is in glycidyl methacrylate of the present invention (GMA) and vinylbenzene (St) two kinds of monomers and polyphenylene oxide under initiator effect, generate a kind of high performance functional polyphenylene ether graft copolymer, i.e. PPO grafting GMA and St multipolymer (PPO-g-(GMA-St)), containing double bond and ester group in its molecular structure, special in carrying out with other functional groups many epoxide group that reacts, can with the radical reaction such as carboxyl, hydroxyl, acid anhydrides and amine; And GMA is as active reactive monomer, under general condition can with various of monomer generation copolymerization, particularly with can increase substantially its grafting efficiency in the polymer during styrene-grafted; In addition, the end amido of the active epoxide group contained in its molecule more easily and in nylon or carboxyl generation chemical reaction.Using the reactive compatibilizer of this multipolymer as PPO/PA alloy system, it significantly can improve the consistency of PPO/PA alloy, and improves mechanical property and the water tolerance of PPO/PA alloy, and industrial application is all right.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of fusion-grafting multipolymer [PPO-g-(GMA-St)] of the fusion-grafting multipolymer (PPO-g-GMA) of PPO, PPO and GMA in the embodiment of the present invention, PPO and GMA, St, wherein, a is PPO, b is PPO-g-GMA, c is PPO-g-(GMA-St).
Embodiment
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
One, PPO/PA alloy modification expanding material is prepared
(1) glycidyl methacrylate (GMA) and vinylbenzene (St) are configured to mixed solution according to mass ratio 1:1, then the initiator dicumyl peroxide (DCP) accounting for grafted monomer total amount 5% is joined in grafted monomer mixed solution dissolve;
(2) polyphenylene oxide PPO and grafted monomer mixed solution are placed in stirrer and fully mix 5-10min, wherein grafted monomer mixed solution accounts for 8% of total mixed solution weight;
(3) the total mixed solution after mixing is joined melting graft reaction in torque rheometer, temperature of reaction 220-250 DEG C, rotating speed 50-70rpm, the reaction times is 6-10min.
(4) reaction terminate after by material cooled, then with pulverizer pulverize, obtain the particle that percentage of grafting is the functional polyphenylene ether graft copolymer of 2.4%, i.e. PPO/PA alloy modification expanding material.
The infrared spectrogram of the fusion-grafting multipolymer [PPO-g-(GMA-St)] of the fusion-grafting multipolymer (PPO-g-GMA) of PPO, PPO and GMA, PPO and GMA, St as shown in Figure 1.
As seen from Figure 1: compared with pure PPO, 1730cm in the infrared spectra of fusion-grafting product P PO-g-GMA and PPO-g-(GMA-St)
-1near all there is a new absorption peak, this peak is the stretching vibration absorption peak of carbonyl (C=O) in GMA molecule.This illustrates that GMA is successfully grafted on PPO chain.Also can find out that in the grafts not adding St monomer, the absorption peak of GMA is more weak, area is also little especially, illustrates that the GMA be grafted on PPO macromolecular chain is less simultaneously.After introducing St in grafting system, find at 1730cm
-1the characteristic absorbance peak area of place GMA obviously increases.
The method of calculation of expanding material percentage of grafting are as follows:
Accurate weighing grafts sample 0.45g, puts in the flask that 50mL toluene is housed, and reflux, to dissolving completely and being cooled to less than 60 DEG C, accurately moves into the KOH-ethanolic soln that 25mL concentration is 0.05mol/L, continues reflux 4h.To be cooled to room temperature, using phenolphthalein as indicator, be titrated to terminal with the HCl-Virahol standardized solution that concentration is 0.05mol/L.
Percentage of grafting calculation formula:
In formula: c is HCl-Virahol concentration of standard solution (mol/L);
M is the quality (g) of grafts;
V is the standardized solution volume (mL) that sample titration consumes;
V
0for the standardized solution volume (mL) that blank titration consumes;
M is the molar mass (g/mol) of GMA;
Chemical titration PPO-g-(GMA-St) percentage of grafting is 2.4%, and PPO-g-GMA percentage of grafting is only 0.8%.
Two, PPO/PA alloy is prepared
Formula and the processing conditions of PPO/PA alloy are as shown in table 1.Products therefrom is tested notched Izod impact strength according to GB1043-93 by the present invention, according to GB1040-89 test tensile strength, tests water-intake rate according to GB/T1034-1998.All test results are in table 1.
Table 1 materials Example 1 ~ 6 of the present invention component formula, processing conditions and product performance
From upper table 1, shock strength, the tensile strength of functional polyphenylene ether graft copolymer capacity increasing modifying PPO/PA alloy material of the present invention all obtain larger raising than the PPO/PA alloy of non-capacity increasing modifying, have excellent toughness and intensity.And the water-intake rate of functional polyphenylene ether graft copolymer capacity increasing modifying PPO/PA alloy material of the present invention is more much lower than the PPO/PA alloy of non-capacity increasing modifying, thus improves the water-absorbent of material, expands the range of application of PPO/PA alloy material.
Claims (4)
1. a PPO/PA alloy, is characterized in that being made up of following weight component:
Described oxidation inhibitor is polyphenol antioxidant 1010;
Described expanding material is polyphenylene oxide, glycidyl methacrylate and cinnamic graft copolymer, and the preparation method of this graft copolymer is as follows:
(1) glycidyl methacrylate and vinylbenzene are configured to mixed solution according to weight ratio 1:1, then the initiator accounting for grafted monomer total amount 4 ~ 6% is joined in mixed solution dissolve, obtain grafting mixed solution;
(2) polyphenylene oxide and described grafting mixed solution are fully mixed 5 ~ 10min, obtain total mixed solution; Wherein grafting mixed solution accounts for 6 ~ 10% of total mixed solution weight;
(3) joined in torque rheometer by described total mixed solution carry out melting graft reaction at 50-70rpm, 220-250 DEG C, the reaction times is 6-10min;
(4) reaction terminate after by material cooled, then with pulverizer pulverize, namely obtain granular PPO/PA alloy modification expanding material.
2. PPO/PA alloy as claimed in claim 1, is characterized in that: described initiator is dicumyl peroxide.
3. PPO/PA alloy according to claim 1, it is characterized in that described polyphenylene oxide is the nonpolar linear polymer carrying out oxidative dimerization with oxygen by 2,6-xylenols under the effect of copper-ammonium catalyzer and obtain, is contain in molecular backbone chain
the thermoplastic engineering plastic of chain link.
4. the preparation method of PPO/PA alloy as claimed in claim 1, is characterized in that comprising the steps:
The dry 12-24h at 80 ~ 90 DEG C by polyphenylene oxide and nylon, then after polyphenylene oxide, nylon and expanding material being stirred 5-10min in agitator, join in torque rheometer 230-250 DEG C, rotating speed carries out melt blending under being 50-70rpm, reaction times is 10-15min, can obtain the block PPO/PA alloy material of functional polyphenylene ether graft copolymer capacity increasing modifying.
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| CN201310102133.5A CN103146176B (en) | 2013-03-27 | 2013-03-27 | Modification compatibilizer of PPO/PA (Poly-p-phenylene oxide/polyacrylate) alloy and PPO/PA alloy |
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| CN201310102133.5A CN103146176B (en) | 2013-03-27 | 2013-03-27 | Modification compatibilizer of PPO/PA (Poly-p-phenylene oxide/polyacrylate) alloy and PPO/PA alloy |
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| CN103146176B true CN103146176B (en) | 2015-01-07 |
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| CN104844767A (en) * | 2015-05-21 | 2015-08-19 | 广东威林工程塑料有限公司 | Toughening compatilizer containing polyphenyl ether and polyamide |
| CN112521747B (en) * | 2020-12-08 | 2022-02-01 | 安徽江淮汽车集团股份有限公司 | PA66 composite material and preparation method and application thereof |
| CN114106263A (en) * | 2021-12-29 | 2022-03-01 | 广东聚航新材料研究院有限公司 | Methacrylate functionalized polyphenyl ether and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1420911A (en) * | 1999-11-12 | 2003-05-28 | 通用电气公司 | Conductive polyphenylene ether-polyamide blend |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1420911A (en) * | 1999-11-12 | 2003-05-28 | 通用电气公司 | Conductive polyphenylene ether-polyamide blend |
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