CN109851968B - Ultrahigh melt strength blow molding resin composition and preparation method thereof - Google Patents
Ultrahigh melt strength blow molding resin composition and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an ultrahigh melt strength blow molding resin composition and a preparation method thereof, wherein the composition is prepared from the following raw materials in parts by weight: 40-60 parts of PMMA resin, 30-40 parts of ASA resin, 10-20 parts of MMA-St-MAH copolymer resin, 1-5 parts of cross-linking agent, 0.3-1.0 part of black toner, 0.6-1.5 parts of processing aid and 0.3-1.5 parts of weather-resistant agent, and the raw materials are premixed in a high-speed mixer for 3-10 minutes to obtain the PMMA/ASA resin composition with ultrahigh melt strength. Compared with the prior art, the invention has the advantages of ultrahigh melt strength, excellent comprehensive performance and the like, has the appearance effect of piano black and excellent weather resistance and scratch resistance, and is very suitable for blow molding of parts such as automobile empennages, spoilers and the like which are free of spraying highlight piano black.
Description
Technical Field
The invention relates to the technical field of high polymer material processing, in particular to an ultrahigh melt strength blow molding resin composition and a preparation method thereof.
Background
The automobile empennage and spoiler are usually prepared by blow molding, the material for blow molding is mainly ABS resin, and high melt strength and heat resistance are required besides good mechanical properties, but the weather resistance of the ABS cannot meet the requirements of automobile exterior trim, so the weather resistance of the ABS needs to be compensated by a two-step paint spraying method. The paint spraying process is complex, low in efficiency, high in cost and large in environmental pollution.
The PMMA/ASA resin has excellent impact resistance, weather resistance and excellent coloring performance, and can be added with different toners to obtain various colors. Since PMMA/ASA resin can obtain transparent substrate by proper compatilizer selection and component refractive index matching, appearance effect of high-gloss piano black can be obtained by dyeing with dye black (CN 106046643B). In the years, PMMA/ASA can replace piano black paint to achieve substantial cost reduction, so the PMMA/ASA can be widely applied to parts such as grilles, rearview mirror shells, upright post decorative plates and the like of automobiles. PMMA/ASA resins cannot be used for blow molding because of their low melt strength. There are generally two approaches to increasing melt strength: firstly, selecting a high molecular weight resin matrix; second, the resin matrix is moderately crosslinked. For PMMA/ASA resins, the commercially available PMMA has a weight average relative molecular mass of 30,000-150,000g/mol, and if the molecular weight is increased further, the processing temperature of the resin is higher than the decomposition temperature and cannot be processed. Crosslinking PMMA can increase the melt strength of PMMA/ASA resins, but in contrast, crosslinking occurs which causes the PMMA/ASA resin to lose the high gloss, piano black effect, such a material cannot replace the piano black paint effect.
Many patents, such as CN106046643B, CN107841077A and CN 107501829 a, report methods for preparing injection molding grade PMMA/ASA resins, which have good flowability and low melt strength for molding large parts, and thus are not suitable for blow molding. No report is found about the ultrahigh melt strength blow molding grade PMMA/ASA resin composition and the preparation method thereof at present.
Disclosure of Invention
The present invention is directed to overcoming the above-mentioned drawbacks of the prior art and providing an ultrahigh melt strength blow-molded PMMA/ASA resin composition and a method for preparing the same.
The purpose of the invention can be realized by the following technical scheme:
the ultrahigh melt strength blow molding resin composition is prepared from the following raw materials in parts by weight:
40-60 parts of PMMA resin, 30-40 parts of ASA resin, 10-20 parts of MMA-St-MAH copolymer resin, 1-5 parts of cross-linking agent, 0.3-1.0 part of black toner, 0.6-1.5 parts of processing aid and 0.3-1.5 parts of weather resisting agent.
Preferably, the PMMA resin has a weight average relative molecular mass of 80,000-150,000. The high molecular weight PMMA is selected to increase the melt strength of the composition and thereby achieve blow molding stability. If the molecular weight is further increased, the blow molding temperature can exceed 270 ℃, PMMA material is easy to degrade, silver wires appear on a blow molded part, and the highlight effect of piano black is influenced; if the molecular weight is too low, the melt strength of the composition is too low and the blow molding effect cannot be achieved.
Preferably, the ASA resin has a refractive index in the range of 1.50 to 1.53 and a rubber weight fraction of 40% to 60%. The ASA with the refractive index is blended with PMMA and MMA-St-MAH, and the transmittance of the blend can be more than or equal to 60% under the condition of no toner, which is the premise that the dye black is dyed into piano black.
Preferably, the MMA-St-MAH copolymer resin contains 20-30 wt% of maleic anhydride and has a refractive index of 1.52-1.54. The maleic anhydride content is selected in relation to its refractive index, which is selected to obtain a ternary ASA/PMMA/MMA-St-MAH blend as a natural color substrate with a transmittance of 60% or more to obtain the appearance of piano black.
Preferably, the crosslinking assistant is one or more of toluene diisocyanate, diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate, lysine diisocyanate and lysine triisocyanate.
Preferably, the black toner is dye black.
Preferably, the processing aid comprises an antioxidant, a lubricant and/or a mold release agent.
Preferably, the antioxidant is a hindered phenol antioxidant or a phosphite antioxidant, the lubricant is pentaerythritol stearate or ethylene bis-stearamide, and the release agent is a silicone release agent.
Preferably, the weather resisting agent is one or more of salicylate, benzophenone, UV absorbent of benzotriazole class and hindered amine class free radical scavenger.
The preparation method of the ultrahigh melt strength blow molding resin composition comprises the following steps:
(1) preparing materials according to the following components and contents:
40-60 parts of PMMA resin, 30-40 parts of ASA resin, 10-20 parts of MMA-St-MAH copolymer resin, 1-5 parts of cross-linking agent, 0.3-1.0 part of black toner, 0.6-1.5 parts of processing aid and 0.3-1.5 parts of weather-resistant agent;
(2) premixing the raw materials in the step (1) in a high-speed mixer;
(3) and (3) melting and extruding the premix obtained in the step (2) through a double-screw extruder at the extrusion temperature of 180-250 ℃ and the screw rotating speed of 200-500 r/min, and cooling and granulating to obtain the PMMA/ASA resin composition for blow molding with ultrahigh melt strength.
Compared with the prior art, the invention has the following advantages:
1. the invention adopts a technical means of reaction blending, and under the initiation of an isocyanate crosslinking assistant, maleic anhydride groups in PMMA-St-MAH resin generate macromolecular free radical reaction in the extrusion granulation process to generate long-chain branched or micro-crosslinked PMMA, thereby obviously improving the melt strength of the system and preparing the PMMA/ASA resin composition with no surface defect, high strength, high toughness and high dimensional stability and ultrahigh melt strength;
2. the optimized PMMA modified resin PMMA-St-MAH and the proper type and dosage of the cross-linking agent ensure that the cross-linking reaction is properly carried out, so that the surface of a blow-molded product of the resin composition has the effect of high gloss piano black;
3. the preparation method has the advantages of simple process, low cost, high and stable melt strength in the processing process, and is very suitable for industrial production.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The ultrahigh melt strength blow molding resin composition is prepared from the following raw materials in parts by weight: 40-60 parts of PMMA resin, 30-40 parts of ASA resin, 10-20 parts of MMA-St-MAH copolymer resin, 1-5 parts of cross-linking agent, 0.3-1.0 part of black toner, 0.6-1.5 parts of processing aid and 0.3-1.5 parts of weather resisting agent.
In the above raw material composition, the weight average relative molecular mass of the PMMA resin was 80,000-150,000. The ASA resin has a refractive index in the range of 1.50-1.53 and a rubber weight fraction of 40% -60%. The MMA-St-MAH copolymer resin contains 20-30 wt% of maleic anhydride and has a refractive index of 1.52-1.54.
The crosslinking assistant is one or more of toluene diisocyanate, diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate, lysine diisocyanate and lysine triisocyanate. The specific isocyanate crosslinking auxiliaries can initiate maleic anhydride groups in the PMMA-St-MAH resin to generate macromolecular free radical reaction in the extrusion granulation process, and long-chain branched or micro-crosslinked PMMA is generated, so that the melt strength of the system is remarkably improved. The black toner is dye black. The processing aid may include an antioxidant, a lubricant and/or a mold release agent as required. The antioxidant used may be hindered phenol type antioxidant or phosphite type antioxidant, the lubricant may be pentaerythritol stearate or ethylene bis-stearamide, and the mold release agent may be silicone type mold release agent. The weather resisting agent is one or more of salicylate, benzophenone, benzotriazole UV absorbent and hindered amine free radical scavenger.
The ultrahigh melt strength blow molding resin composition is prepared by the following steps:
(1) preparing materials according to the formula;
(2) premixing the raw materials in the step (1) in a high-speed mixer;
(3) and (3) melting and extruding the premix obtained in the step (2) through a double-screw extruder at the extrusion temperature of 180-250 ℃ and the screw rotating speed of 200-500 r/min, and cooling and granulating to obtain the PMMA/ASA resin composition for blow molding with ultrahigh melt strength.
The following are more detailed embodiments, and the technical solutions and the technical effects obtained by the present invention will be further described by the following embodiments.
Example 1
Composition of raw materials
Example 2
Composition of raw materials
Example 3
Composition of raw materials
Example 4
Composition of raw materials
Example 5
Composition of raw materials
Example 6
Composition of raw materials
Comparative example 1
Composition of raw materials
Comparative example 1 the crosslinker in example 1 was removed and the rest were identical.
Comparative example 2
Composition of raw materials
Comparative example 1 PMMA was changed to low molecular weight PMMA according to example 1, the others being identical.
Comparative example 3 raw material composition
Comparative example 3 the amounts of PMMA resin and MMA-St-MAH resin were varied according to example 4, and the other was completely identical.
Comparative example 4
Composition of raw materials
Comparative example 4 according to example 4, MMA-St-MAH resin was changed to SMA resin, and others were completely identical.
Comparative example 5
Composition of raw materials
Comparative example 5 the refractive index of the ASA resin was changed to 1.49 according to example 6, and the others were completely identical;
the above PMMA/ASA resin composition has the same preparation method and comprises the following steps:
(1) preparing the materials according to the components and the contents;
(2) premixing the materials prepared in the step (1) in a high-speed mixer;
(3) and (3) melting and extruding the premix obtained in the step (2) through a double-screw extruder at the extrusion temperature of 230 ℃ and the screw rotating speed of 300 revolutions per minute, and cooling and granulating to obtain the PMMA/ASA resin composition for blow molding with ultrahigh melt strength.
Performance evaluation method and implementation standard thereof
And (3) testing mechanical properties:
the ultra-high melt strength PMMA/ASA resin compositions prepared in examples 1 to 6 and comparative examples 1 to 5 were subjected to mechanical property tests, and the surface of the blow-molded article was observed to evaluate the gloss and L value, and the degree of blackness of the surface, the results of which are shown in Table 1:
charpy notched impact strength: the impact energy is 4J according to the test of ISO 179-1:2010 (E);
vicat softening point: testing according to ISO 306:2013(E) standard under the test condition of 5Kg at 50 ℃/h;
flexural modulus: testing according to ISO 178:2010(E) standard, wherein the testing speed is 2 mm/min;
melt index: the test conditions were 220 ℃ 10Kg, according to ISO 1133-1:2011 (E).
Gloss: the injection molded plaques were tested at an angle of 20 ℃ according to ASTM D2457 using a Konika Meter Multigloss 268 gloss Meter.
TABLE 1 mechanical Property test and blow molded article surface results
Example 7
The ultrahigh melt strength blow molding resin composition is prepared from the following raw materials in parts by weight: PMMA resin 40, ASA resin 40, MMA-St-MAH copolymer resin 20, cross-linking agent 1, black toner 0.3, processing aid 0.6 and weather-resistant agent 0.3.
In the above raw material composition, the weight average relative molecular mass of the PMMA resin was 80,000. The ASA resin had a refractive index of 1.50 and a rubber weight fraction of 40%. The MMA-St-MAH copolymer resin contains 20% by weight of maleic anhydride and has a refractive index of 1.52. The crosslinking assistant used is a mixture of toluene diisocyanate and diphenylmethane diisocyanate. The processing aid adopts hindered phenol antioxidant and pentaerythritol stearate lubricant, and the weather resisting agent is salicylate.
The ultrahigh melt strength blow molding resin composition is prepared by the following steps:
(1) preparing materials according to the formula;
(2) premixing the raw materials in the step (1) in a high-speed mixer;
(3) and (3) melting and extruding the premix obtained in the step (2) through a double-screw extruder at the extrusion temperature of 180 ℃ and the screw rotating speed of 500 rpm, and cooling and granulating to obtain the PMMA/ASA resin composition for blow molding with ultrahigh melt strength.
Example 8
The ultrahigh melt strength blow molding resin composition is prepared from the following raw materials in parts by weight: 60 parts of PMMA resin, 30 parts of ASA resin, 10 parts of MMA-St-MAH copolymer resin, 5 parts of cross-linking agent, 1.0 part of black toner, 1.5 parts of processing aid and 1.5 parts of weather resisting agent.
In the above raw material composition, the weight average relative molecular mass of the PMMA resin was 150,000. The ASA resin had a refractive index of 1.53 and a rubber weight fraction of 60%. The weight fraction of maleic anhydride in the MMA-St-MAH copolymer resin was 30%, the weight average relative molecular mass of the resin was 100,000, and the refractive index was 1.54. The crosslinking assistant used is lysine triisocyanate. The processing aid is a silicone release agent, and the weather-resistant agent is a mixture of UV absorbers such as benzophenone and benzotriazole.
The ultrahigh melt strength blow molding resin composition is prepared by the following steps:
(1) preparing materials according to the formula;
(2) premixing the raw materials in the step (1) in a high-speed mixer;
(3) and (3) melting and extruding the premix obtained in the step (2) through a double-screw extruder at the extrusion temperature of 250 ℃ and the screw rotating speed of 200-500 r/min, and cooling and granulating to obtain the PMMA/ASA resin composition for blow molding with ultrahigh melt strength.
In the preparation method, the MMA-St-MAH resin is subjected to macromolecular reaction in the extrusion granulation process by adopting a reaction extrusion blending method, so that the PMMA/ASA resin with ultrahigh melt strength and excellent comprehensive performance is prepared, and the resin composition also has the appearance effect of piano black and excellent weather resistance and scratch resistance, and is very suitable for blow molding of parts such as automobile empennages, spoilers and the like which are free of spraying highlight piano black.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (7)
1. The ultrahigh melt strength blow molding resin composition is characterized by being prepared from the following raw materials in parts by weight:
40-60 parts of PMMA resin, 30-40 parts of ASA resin, 10-20 parts of MMA-St-MAH copolymer resin, 1-5 parts of cross-linking agent, 0.3-1.0 part of black toner, 0.6-1.5 parts of processing aid and 0.3-1.5 parts of weather resisting agent;
the weight average relative molecular mass of the PMMA resin is 80,000-150,000;
the ASA resin has a refractive index ranging from 1.50 to 1.53 and a rubber weight fraction of 40 to 60 percent;
the cross-linking agent is one or more of toluene diisocyanate, diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate, lysine diisocyanate and lysine triisocyanate.
2. The ultrahigh melt strength blow molding resin composition as claimed in claim 1, wherein the weight fraction of maleic anhydride in said MMA-St-MAH copolymer resin is 20-30% and the refractive index is 1.52-1.54.
3. The ultrahigh melt strength blow molding resin composition as claimed in claim 1 wherein said black toner is a dye black.
4. The ultrahigh melt strength blow molding resin composition as claimed in claim 1 wherein said processing aid comprises an antioxidant, a lubricant and/or a mold release agent.
5. The ultrahigh melt strength blow molding resin composition as claimed in claim 4, wherein said antioxidant is a hindered phenolic antioxidant or a phosphite antioxidant, said lubricant is pentaerythritol stearate or ethylene bis stearamide, and said mold release agent is a silicone-based mold release agent.
6. The ultrahigh melt strength blow molding resin composition as claimed in claim 1 wherein said weathering agent is one or more of salicylate, benzophenone, benzotriazole type UV absorbers and hindered amine type radical scavengers.
7. The process for preparing an ultrahigh melt strength blow molding resin composition according to claim 1, wherein the process comprises the steps of:
(1) preparing materials according to the following components and contents:
40-60 parts of PMMA resin, 30-40 parts of ASA resin, 10-20 parts of MMA-St-MAH copolymer resin, 1-5 parts of cross-linking agent, 0.3-1.0 part of black toner, 0.6-1.5 parts of processing aid and 0.3-1.5 parts of weather-resistant agent;
(2) premixing the raw materials in the step (1) in a high-speed mixer;
(3) and (3) melting and extruding the premix obtained in the step (2) through a double-screw extruder at the extrusion temperature of 180-250 ℃ and the screw rotating speed of 200-500 r/min, and cooling and granulating to obtain the PMMA/ASA resin composition for blow molding with ultrahigh melt strength.
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| CN111117129A (en) * | 2019-12-23 | 2020-05-08 | 上海普利特复合材料股份有限公司 | Blow molding PMMA/ASA resin with ultrahigh melt strength and preparation method thereof |
| CN111690222B (en) * | 2020-07-09 | 2022-05-10 | 东莞市奥能工程塑料有限公司 | High-heat-resistance high-brightness PMMA/ASA alloy material and preparation method and application thereof |
| CN113088013B (en) * | 2021-05-20 | 2022-07-15 | 上海金山锦湖日丽塑料有限公司 | UVC-resistant ASA resin composition and preparation method thereof |
| CN114316424B (en) * | 2021-11-22 | 2023-08-25 | 金发科技股份有限公司 | Transparent weather-proof PP/PS composite material and preparation method thereof |
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| CN106832723B (en) * | 2017-03-20 | 2019-07-19 | 四川中物材料股份有限公司 | A kind of high heat resistance high durable ASA/PMMA composite material and preparation method |
| CN107841077B (en) * | 2017-11-09 | 2020-04-21 | 银禧工程塑料（东莞）有限公司 | Heat-resistant transparent PMMA/ASA alloy material and preparation method thereof |
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