CN109851968A - A kind of superelevation melt strength blow molding resins composition and preparation method thereof - Google Patents
A kind of superelevation melt strength blow molding resins composition and preparation method thereof Download PDFInfo
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- CN109851968A CN109851968A CN201811621771.7A CN201811621771A CN109851968A CN 109851968 A CN109851968 A CN 109851968A CN 201811621771 A CN201811621771 A CN 201811621771A CN 109851968 A CN109851968 A CN 109851968A
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Abstract
The present invention relates to a kind of superelevation melt strength blow molding resins compositions and preparation method thereof, it is prepared using the raw material of following components and parts by weight content: PMMA resin 40-60, ASA resin 30-40, MMA-St-MAH copolymer resins 10-20, crosslinking agent 1-5, black toner 0.3-1.0, processing aid 0.6-1.5, weather resisting agent 0.3-1.5, above-mentioned raw material are premixed 3-10 minutes in high-speed mixer, then the pre- PMMA/ASA resin combination that superelevation melt strength can be obtained.Compared with prior art, the present invention has many advantages, such as superelevation melt strength, excellent combination property, also there is the black appearance of piano and excellent weather-proof, scraping and wiping resistance performance, be highly suitable for blow molding and exempt to spray the products such as bloom piano black automobile tail fin, spoiler.
Description
Technical field
The present invention relates to technical field of polymer material processing, more particularly, to a kind of superelevation melt strength blow molding resins group
Close object and preparation method thereof.
Background technique
Automobile tail fin and spoiler generally use blow molding processing preparation, and the material for blow molding is mainly ABS resin,
Other than requiring good mechanical performance, high melt strength and heat resistance it is also desirable to have, but ABS is due to weatherability
It is not able to satisfy the requirement of automobile exterior, so needing to make up the weatherability of ABS by the method for two procedures spray painting.And it paints
It is complex process, low efficiency, at high cost, it causes serious pollution to the environment.
PMMA/ASA resin has excellent shock resistance, weather resistance and outstanding tinctorial property, can be added
Different toners obtains various colors.Since PMMA/ASA resin can be selected and component refractive index by compatilizer appropriate
Cooperation obtains transparent substrate, can obtain the black appearance of bloom piano (CN106046643B) by the black dyeing of dyestuff.This
The alternative piano dirty oil paint of several years PMMA/ASA realizes that significantly drop is originally, therefore is widely used in the grid of automobile, rearview mirror
On the parts such as shell, pillar trim plate.Since the melt strength of PMMA/ASA resin is lower, cannot be used to be blow molded.Generally
Improving melt strength, there are two schemes: first, select the resin matrix of high molecular weight；Second, keep resin matrix appropriately crosslinked.It is right
For PMMA/ASA resin, the average weight-molecular mass of commercially available PMMA is 30,000-150,000g/mol, if molecule
Amount improves again can make the processing temperature of resin be higher than decomposition temperature, without being capable of processing.Make PMMA crosslinking that PMMA/ASA can be improved
The melt strength of resin, but paradoxically with this, it is black that the generation of crosslinking can make PMMA/ASA resin lose high glaze, piano
Effect, such material cannot replace the effect of piano dirty oil paint.
Many patents such as 107501829 A of CN106046643B, CN107841077A and CN etc. report injection grade
The preparation method of PMMA/ASA resin, these PMMA/ASA resins are in order to form big part, therefore mobility is preferable, melt strength
It is very low, so being not particularly suited for blow molding process.Grade PMMA/ASA resin combination and its preparation are blow molded about superelevation melt strength
Method yet there are no report.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of superelevation melt strengths
It is blow molded PMMA/ASA resin combination and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of superelevation melt strength blow molding resins composition, is prepared into using the raw material of following components and parts by weight content
It arrives:
PMMA resin 40-60, ASA resin 30-40, MMA-St-MAH copolymer resins 10-20, crosslinking agent 1-5, black toner
0.3-1.0, processing aid 0.6-1.5, weather resisting agent 0.3-1.5.
Preferably, the average weight-molecular mass of the PMMA resin is 80,000-150,000.Select high molecular weight
The purpose of PMMA is the melt strength in order to improve composition, to realize the stability of blow molding.If molecular weight further mentions
Height, blow molding processing temperature can be more than 270 DEG C, and PMMA material is easy degradation and occurs filamentary silver on blown plastic articles, and it is black to influence piano
Bloom effect；If molecular weight is too low, the melt strength of composition is relatively low, also cannot achieve blow molding effect.
Preferably, the ranges of indices of refraction of the ASA resin is in 1.50-1.53, rubber weight fraction 40%-60%.This
It is blended together with the ASA and PMMA and MMA-St-MAH of one refractive index, in the case where no toner, the transmitance of the blend
It can accomplish >=60%, this condition, which is that dyestuff is black, dyes the black premise of piano.
Preferably, maleic anhydride weight fraction is 20-30% in the MMA-St-MAH copolymer resin, and refractive index exists
1.52-1.54.The selection of this maleic anhydride content is related to its refractive index, and the selection of this refractive index is then to obtain
ASA/PMMA/MMA-St-MAH ternary blends are the true qualities substrate of transmitance >=60%, to obtain the black appearance of piano.
Preferably, the cross-linking aid is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, 1,6- oneself two isocyanides
Acid esters, lysine diisocyanate, the one or more of lysine triisocyanate.
Preferably, the black toner is that dyestuff is black.
Preferably, the processing aid includes antioxidant, lubricant and/or release agent.
Preferably, the antioxidant is Hinered phenols antioxidant or phosphite ester antioxidant, and the lubricant is season penta
Tetrol stearate or ethylene bis stearic acid amide, the release agent are silicone release agent.
Preferably, weather resisting agent is that salicylate, benzophenone, the UV absorbent of benzotriazole and hindered amines are free
Base agent for capturing it is one or more.
The preparation method of superelevation melt strength blow molding resins composition, using following steps:
(1) it stocks up by following components and content:
PMMA resin 40-60 parts by weight, ASA resin 30-40 parts by weight, MMA-St-MAH copolymer resins 10-20 parts by weight,
Crosslinking agent 1-5 parts by weight, black toner 0.3-1.0 parts by weight, processing aid 0.6-1.5 parts by weight, weather resisting agent 0.3-1.5 weight
Part；
(2) raw material in step (1) is premixed in super mixer；
(3) by premix obtained in step (2) by double screw extruder, in 180-250 DEG C of extrusion temperature and 200-
Melting extrusion is carried out under the conditions of 500 revs/min of screw speed, cooling granulation obtains the blow molding PMMA/ of superelevation melt strength
ASA resin composition.
Compared with prior art, the invention has the following advantages that
1, the present invention uses the technological means of reactive blending, makes PMMA-St- under the initiation of isocyanates cross-linking aid
Macromolecular radical reaction occurs during extruding pelletization for the maleic groups in MAH resin, generates long chain branching or micro-
The PMMA of crosslinking, to improve the melt strength of system significantly, prepare surface zero defect and there is high-intensitive, high-ductility
The superelevation melt strength PMMA/ASA resin combination of property, high-dimensional stability；
2, currently preferred PMMA modified resin PMMA-St-MAH and suitable type of crosslinking agent and dosage guarantee
The appropriateness of cross-linking reaction carries out, and so that the resin combination blow molded product surface is had the effect of that bloom piano is black；
3, preparation method technical process of the invention is simple, at low cost, and melt strength is high in process and stablizes, very
It is suitble to industrialized production.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
A kind of superelevation melt strength blow molding resins composition, is prepared into using the raw material of following components and parts by weight content
It arrives: PMMA resin 40-60, ASA resin 30-40, MMA-St-MAH copolymer resins 10-20, crosslinking agent 1-5, black toner 0.3-
1.0, processing aid 0.6-1.5, weather resisting agent 0.3-1.5.
In above-mentioned raw materials composition, the average weight-molecular mass of PMMA resin is 80,000-150,000.The folding of ASA resin
Rate range is penetrated in 1.50-1.53, rubber weight fraction 40%-60%.Maleic anhydride weight in MMA-St-MAH copolymer resin
Amount score is 20-30%, and refractive index is in 1.52-1.54.
The cross-linking aid used be toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, hexamethylene diisocyanate,
Lysine diisocyanate, the one or more of lysine triisocyanate.Above-mentioned several specific isocyanate-crosslinked auxiliary agents
The maleic groups in PMMA-St-MAH resin can be caused, macromolecular radical reaction occurs during extruding pelletization,
The PMMA for generating long chain branching or micro- crosslinking, to improve the melt strength of system significantly.Black toner is that dyestuff is black.Add
Work auxiliary agent, which can according to need to use, includes antioxidant, lubricant and/or release agent.It is anti-that the antioxidant used can be Hinered phenols
Oxygen agent or phosphite ester antioxidant, lubricant can be pentaerythritol stearate or ethylene bis stearic acid amide, release agent
It can be silicone release agent.Weather resisting agent is the UV absorbent and hindered amines of salicylate, benzophenone, benzotriazole
Free radical scavenger it is one or more.
Superelevation melt strength blow molding resins composition is prepared using following steps:
(1) it stocks up according to above-mentioned formula composition；
(2) raw material in step (1) is premixed in super mixer；
(3) by premix obtained in step (2) by double screw extruder, in 180-250 DEG C of extrusion temperature and 200-
Melting extrusion is carried out under the conditions of 500 revs/min of screw speed, cooling granulation obtains the blow molding PMMA/ of superelevation melt strength
ASA resin composition.
More detailed case study on implementation below, by following case study on implementation further illustrate technical solution of the present invention with
And the technical effect that can be obtained.
Embodiment 1
Raw material composition
Embodiment 2
Raw material composition
Embodiment 3
Raw material composition
Embodiment 4
Raw material composition
Embodiment 5
Raw material composition
Embodiment 6
Raw material composition
Comparative example 1
Raw material composition
Comparative example 1 removes crosslinking agent in embodiment 1, other are completely the same.
Comparative example 2
Raw material composition
For comparative example 1 according to embodiment 1, PMMA is changed to low molecular weight PMMA, other are completely the same.
3 raw material of comparative example composition
Comparative example 3 changes the amount of PMMA resin and MMA-St-MAH resin, other are completely the same according to embodiment 4.
Comparative example 4
Raw material composition
Comparative example 4 is SMA resin according to embodiment 4, change MMA-St-MAH resin, other are completely the same.
Comparative example 5
Raw material composition
Comparative example 5 is according to embodiment 6, and the refractive index for changing ASA resin is 1.49, other are completely the same；
The preparation method of the above PMMA/ASA resin combination is identical, and the following steps are included:
(1) it stocks up by said components and content；
(2) material got ready in step (1) is premixed in super mixer；
(3) by premix obtained in step (2) by double screw extruder, in 230 DEG C of extrusion temperatures and 300 revs/min
Melting extrusion is carried out under the conditions of the screw speed of clock, cooling granulation obtains the blow molding PMMA/ASA resin of superelevation melt strength
Composition.
Performance evaluation mode and its implementation standard
Measuring mechanical property:
Superelevation melt strength PMMA/ASA resin combination obtained by embodiment 1-6 and comparative example 1-5 is carried out mechanical
Performance test, and blow-molded article surface is observed, gloss and the shiny black degree of L value and surface are evaluated, the results are shown in Table 1:
Charpy notch impact strength: according to ISO 179-1:2010 (E) standard testing, impact energy 4J；
Vicat softening point: according to ISO 306:2013 (E) standard testing, test condition 5Kg, 50 DEG C/h；
Bending modulus: according to ISO 178:2010 (E) standard testing, test speed 2mm/min；
Melt index: according to ISO 1133-1:2011 (E) standard testing, test condition is 220 DEG C of * 10Kg.
Glossiness: according to the method for ASTM D2457,268 vancometer of Konica Minolta Multigloss, note are used
Moulding colour table test angle is 20 °.
1 measuring mechanical property of table and blow-molded article surface results
Embodiment 7
A kind of superelevation melt strength blow molding resins composition, is prepared into using the raw material of following components and parts by weight content
Arrive: PMMA resin 40, ASA resin 40, MMA-St-MAH copolymer resins 20, crosslinking agent 1, black toner 0.3, processing aid 0.6,
Weather resisting agent 0.3.
In above-mentioned raw materials composition, the average weight-molecular mass of PMMA resin is 80,000.The refractive index of ASA resin
1.50, rubber weight fraction 40%.Maleic anhydride weight fraction is 20% in MMA-St-MAH copolymer resin, and refractive index exists
1.52.The cross-linking aid used is the mixture of toluene di-isocyanate(TDI), methyl diphenylene diisocyanate.Processing aid uses
Hinered phenols antioxidant and pentaerythritol stearate lubricant, weather resisting agent are salicylate.
Superelevation melt strength blow molding resins composition is prepared using following steps:
(1) it stocks up according to above-mentioned formula composition；
(2) raw material in step (1) is premixed in super mixer；
(3) by premix obtained in step (2) by double screw extruder, in 180 DEG C of extrusion temperatures and 500 revs/min
Melting extrusion is carried out under the conditions of the screw speed of clock, cooling granulation obtains the blow molding PMMA/ASA resin of superelevation melt strength
Composition.
Embodiment 8
A kind of superelevation melt strength blow molding resins composition, is prepared into using the raw material of following components and parts by weight content
Arrive: PMMA resin 60, ASA resin 30, MMA-St-MAH copolymer resins 10, crosslinking agent 5, black toner 1.0, processing aid 1.5,
Weather resisting agent 1.5.
In above-mentioned raw materials composition, the average weight-molecular mass of PMMA resin is 150,000.The refractive index of ASA resin is
1.53, rubber weight fraction 60%.Maleic anhydride weight fraction is 30% in MMA-St-MAH copolymer resin, the weight of resin
Equal relative molecular mass is 100,000, refractive index 1.54.The cross-linking aid used is lysine triisocyanate,.Processing aid
For silicone release agent, weather resisting agent be benzophenone, benzotriazole UV absorbent mixture.
Superelevation melt strength blow molding resins composition is prepared using following steps:
(1) it stocks up according to above-mentioned formula composition；
(2) raw material in step (1) is premixed in super mixer；
(3) by premix obtained in step (2) by double screw extruder, in 250 DEG C of extrusion temperatures and 200-500
Rev/min screw speed under the conditions of carry out melting extrusion, cooling granulation obtains the blow molding PMMA/ASA of superelevation melt strength
Resin combination.
In above-mentioned preparation method, by using the method that is blended of reactive extrursion, MMA-St-MAH during extruding pelletization
Macromolecular reaction occurs between resin, so that the PMMA/ASA resin with superelevation melt strength, excellent combination property is prepared, it should
The appearance and excellent weather-proof, scraping and wiping resistance performance that resin combination also has piano black, are highly suitable for being blow molded into
Type is exempted to spray the products such as bloom piano black automobile tail fin, spoiler.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (10)
1. a kind of superelevation melt strength blow molding resins composition, which is characterized in that using following components and the original of parts by weight content
Material is prepared:
PMMA resin 40-60, ASA resin 30-40, MMA-St-MAH copolymer resins 10-20, crosslinking agent 1-5, black toner 0.3-
1.0, processing aid 0.6-1.5, weather resisting agent 0.3-1.5.
2. a kind of superelevation melt strength blow molding resins composition according to claim 1, which is characterized in that the PMMA tree
The average weight-molecular mass of rouge is 80,000-150,000.
3. a kind of superelevation melt strength blow molding resins composition according to claim 1, which is characterized in that the ASA tree
The ranges of indices of refraction of rouge is in 1.50-1.53, rubber weight fraction 40%-60%.
4. a kind of superelevation melt strength blow molding resins composition according to claim 1, which is characterized in that the MMA-
Maleic anhydride weight fraction is 20-30% in St-MAH copolymer resin, and refractive index is in 1.52-1.54.
5. a kind of superelevation melt strength blow molding resins composition according to claim 1, which is characterized in that the crosslinking helps
Agent is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, relies
The one or more of propylhomoserin triisocyanate.
6. a kind of superelevation melt strength blow molding resins composition according to claim 1, which is characterized in that the black color
Powder is that dyestuff is black.
7. a kind of superelevation melt strength blow molding resins composition according to claim 1, which is characterized in that the processing helps
Agent includes antioxidant, lubricant and/or release agent.
8. a kind of superelevation melt strength blow molding resins composition according to claim 7, which is characterized in that the antioxidant
For Hinered phenols antioxidant or phosphite ester antioxidant, the lubricant is pentaerythritol stearate or the double stearic acid of ethylene
Amide, the release agent are silicone release agent.
9. a kind of superelevation melt strength blow molding resins composition according to claim 1, which is characterized in that the weather resisting agent
For the one or more of salicylate, benzophenone, the UV absorbent of benzotriazole and hindered amines free radical scavenger.
10. a kind of preparation method of superelevation melt strength blow molding resins composition as described in claim 1, which is characterized in that
This method uses following steps:
(1) it stocks up by following components and content:
PMMA resin 40-60 parts by weight, ASA resin 30-40 parts by weight, MMA-St-MAH copolymer resins 10-20 parts by weight, crosslinking
Agent 1-5 parts by weight, black toner 0.3-1.0 parts by weight, processing aid 0.6-1.5 parts by weight, weather resisting agent 0.3-1.5 parts by weight；
(2) raw material in step (1) is premixed in super mixer；
(3) by premix obtained in step (2) by double screw extruder, in 180-250 DEG C of extrusion temperature and 200-500
Rev/min screw speed under the conditions of carry out melting extrusion, cooling granulation obtains the blow molding PMMA/ASA of superelevation melt strength
Resin combination.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111690222A (en) * | 2020-07-09 | 2020-09-22 | 东莞市奥能工程塑料有限公司 | PMMA/ASA alloy material with high heat resistance and high blackness and brightness, preparation method and application thereof |
| CN113088013A (en) * | 2021-05-20 | 2021-07-09 | 上海金山锦湖日丽塑料有限公司 | UVC-resistant ASA resin composition and preparation method thereof |
| CN114316424A (en) * | 2021-11-22 | 2022-04-12 | 金发科技股份有限公司 | Transparent weather-resistant PP/PS composite material and preparation method thereof |
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| CN107841077A (en) * | 2017-11-09 | 2018-03-27 | 银禧工程塑料（东莞）有限公司 | A kind of heat resistant transparent PMMA/ASA alloy materials and preparation method thereof |
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| US6525134B1 (en) * | 1999-09-09 | 2003-02-25 | Atofina | Antistatic acrylic polymer compositions |
| CN106832723A (en) * | 2017-03-20 | 2017-06-13 | 四川中物材料股份有限公司 | A kind of heat-resisting high durable ASA/PMMA composites high and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111690222A (en) * | 2020-07-09 | 2020-09-22 | 东莞市奥能工程塑料有限公司 | PMMA/ASA alloy material with high heat resistance and high blackness and brightness, preparation method and application thereof |
| CN113088013A (en) * | 2021-05-20 | 2021-07-09 | 上海金山锦湖日丽塑料有限公司 | UVC-resistant ASA resin composition and preparation method 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 |
| CN114316424A (en) * | 2021-11-22 | 2022-04-12 | 金发科技股份有限公司 | Transparent weather-resistant PP/PS composite material 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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