CN114044966A - Anti-fogging polypropylene composition and preparation method and application thereof - Google Patents
Anti-fogging polypropylene composition and preparation method and application thereof Download PDFInfo
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- CN114044966A CN114044966A CN202111228086.XA CN202111228086A CN114044966A CN 114044966 A CN114044966 A CN 114044966A CN 202111228086 A CN202111228086 A CN 202111228086A CN 114044966 A CN114044966 A CN 114044966A
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
Abstract
The invention discloses an anti-fogging polypropylene composition, a preparation method and application thereof, and belongs to the technical field of high polymer materials. The anti-fogging polypropylene composition comprises the following components in parts by weight: 50-100 parts of polypropylene resin, 0-22 parts of toughening agent, 0-10 parts of HDPE, 0-40 parts of filler, 0.1-0.6 part of antioxidant and 0.1-0.5 part of light stabilizer. According to the anti-fogging polypropylene composition, the phenytriazole photostabilizer and/or the high molecular weight hindered amine photostabilizer and the phosphite antioxidant are added in the formula, so that the gloss retention rate of the material after wet atomization testing at 100 ℃ can reach over 90, the anti-fogging effect is excellent, the impact strength of a simple beam notch of the material can reach 42-53, the material has good toughness, and the anti-fogging polypropylene composition can be widely applied to preparation of automotive interior parts.
Description
Technical Field
The invention relates to the technical field of high polymer materials, and particularly relates to an anti-fogging polypropylene composition and a preparation method and application thereof.
Background
Polypropylene (PP) has the advantages of low density, easy processing, excellent mechanical properties, etc., and has been widely used in the fields of automobile industry, home appliances and machinery. For the automotive industry, polypropylene is mainly used for interior and exterior parts of automobiles, such as instrument panels, door panels, pillars and the like, and exterior parts such as bumpers, fenders, deflectors and the like. However, when the polypropylene modified material is used as an automotive interior part, the polypropylene modified material can emit small molecular substances and condense on automotive glass to cause fogging, and the sight line and the driving safety of a driver can be influenced in serious cases. With the improvement of the automobile atomization requirements at home and abroad, the individual host factory puts forward the standard requirements of the amine compounding method atomization and puts forward a new technical subject to the polypropylene material modification factory.
In order to reduce the atomization of polypropylene materials, people carry out deep research on the development and selection of polypropylene, novel processing technology and post-treatment technology, and obtain better and more technical progress. However, these methods are only for the evaluation of the conventional atomization method, i.e., the atomization test under anhydrous conditions, and the gravimetric method and the gloss reflection coefficient method are generally used. Failure occurred when the evaluation of wet atomization was performed. CN104262785A discloses a low odor, high flow, soft touch polyolefin composition and a process for its preparation, the polyolefin composition comprising: 15-30% of polypropylene; 15-50% of hyperbranched polyethylene; 30-60% of a copolymer of ethylene and alpha-olefin; 0.2-1% of antioxidant; 0.2-1% of light stabilizer and 0-3% of other additives, but the optimization of the material still aims at improving the common anti-fogging performance of the polypropylene material under the anhydrous condition, and the wet-process fogging value of the polypropylene material is not improved.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defect and the defect of poor anti-fogging performance of the existing polypropylene composition during evaluation of wet-process atomization, and provides an anti-fogging polypropylene composition, which remarkably improves the wet-process atomization level of the polypropylene composition through the synergistic effect of a specific phosphite antioxidant and a hindered amine light stabilizer.
The invention aims to provide a preparation method of an anti-fogging polypropylene composition.
Still another object of the present invention is to provide a use of the polypropylene composition for the preparation of automotive interior parts.
It is still another object of the present invention to provide an automotive interior part prepared from the polypropylene composition.
The above purpose of the invention is realized by the following technical scheme:
an anti-fogging polypropylene composition comprises the following components in parts by weight:
50-100 parts of polypropylene resin, 0-22 parts of toughening agent, 0-10 parts of HDPE, 0-40 parts of filler, 0.1-0.6 part of antioxidant and 0.1-0.5 part of light stabilizer,
the antioxidant is phosphite ester antioxidant, the light stabilizer is phenytriazole light stabilizer and/or hindered amine light stabilizer with the relative molecular weight more than or equal to 400,
the polypropylene resin is detected according to TSM0503G-2013 composite test B-method amine composite method standard, and the atomization value is not less than 90 under the condition of 100 ℃ for 3 hours.
Among them, it should be noted that:
the contents of the antioxidant and the light stabilizer of the invention must be controlled within the protection range of the invention, the antioxidant effect cannot be achieved when the contents of the antioxidant and the light stabilizer are too low, and the antioxidant and the light stabilizer are easy to precipitate when the contents of the antioxidant and the light stabilizer are too high, thereby affecting the anti-fogging performance.
The polypropylene is used as a basic raw material of the anti-fogging polypropylene composition, the self fogging value is of great importance, the polypropylene resin with the fogging value of more than or equal to 90 under the condition of 100 ℃ for 3 hours is used as the basic raw material according to the standard detection of an amine compounding method of a TSM0503G-2013 composite test B method, and the synergistic effect of the phosphite antioxidant, the benzotriazole light stabilizer and/or the hindered amine light stabilizer with the relative molecular weight of more than or equal to 400 can ensure that the finally prepared polypropylene composition product has good anti-fogging performance, especially good wet fogging level.
The toughening agent of the present invention may be an ethylene-octene copolymer or an ethylene-butene copolymer.
In the actual production of the polypropylene composition, 0.2-1 part by weight of lubricant such as one or more of metal stearate and erucamide can also be included.
The phosphite antioxidant, the benzotriazole light stabilizer and the high molecular weight hindered amine light stabilizer have good chemical stability, good temperature resistance and moisture resistance, high melting point or high molecular weight, are not easily taken away from the surface of PP by polar water molecules, and are not easily separated out at high temperature, and after the phosphite antioxidant and the benzotriazole light stabilizer are added into the polypropylene composition, the precipitation and volatilization of additive micromolecules can be prevented, and the wet atomization level of the polypropylene composition is effectively improved.
The polypropylene composition prepared by the formula can meet the wet atomization test requirement, and is suitable for application in the field of automotive interior parts.
The filler can be one or more of talcum powder, calcium carbonate, whisker or mica, and the average particle size of the filler is 2500-3500 meshes in a conventional selection mode.
Preferably, the composition comprises the following components in parts by weight:
60-80 parts of polypropylene resin, 10-15 parts of toughening agent, 5-8 parts of HDPE, 20-30 parts of filler, 0.2-0.5 part of antioxidant and 0.2-0.3 part of light stabilizer.
Preferably, the antioxidant has a relative molecular weight of 600-1000 and a melting point of 185-230 ℃.
Preferably, the antioxidant is one or more of antioxidant 168 and antioxidant 686.
The phosphite antioxidants have higher melting points and better high-temperature stability, can reduce the precipitation and volatilization of small molecules of the additives, are not easy to precipitate at high temperature, and are beneficial to improving the wet atomization level of the polypropylene composition.
Further preferably, the antioxidant is a compound antioxidant consisting of an antioxidant 168 and an antioxidant 686, wherein the mass ratio of the antioxidant 168 to the antioxidant 686 is 1-2: 1.
The synergistic effect of the antioxidant and the antioxidant can achieve the synergistic antioxidant effect, and the generation of small molecular substances is reduced in the processing process, so that the atomization value is reduced.
Preferably, the light stabilizer is a benzotriazole light stabilizer and/or hindered amine light stabilizer with the relative molecular weight of more than or equal to 800.
Preferably, the light stabilizer is one or more of light stabilizer UV-326, light stabilizer LA-402AF, light stabilizer LA-52 and light stabilizer UV-944.
More preferably, the melting point of the light stabilizer is 120-140 ℃.
The light stabilizers are high in melting point or high in molecular weight, have good high-temperature stability, can reduce precipitation and volatilization of additive micromolecules, are not prone to precipitation at high temperature, are not prone to being taken away from the PP surface by polar water molecules, and are beneficial to improving the wet atomization level of the polypropylene composition.
More preferably, the light stabilizer is a composite light stabilizer consisting of a light stabilizer UV326 and a light stabilizer LA-402AF, wherein the mass ratio of the light stabilizer UV326 to the light stabilizer LA-402AF is 1-2: 1.
The light stabilizer LA-402AF has a large molecular weight, not only has good effects of preventing precipitation and volatilization and is beneficial to improving atomization performance, but also can further improve the compatibility between the light stabilizer UV326 and polypropylene, and is also beneficial to reducing precipitation and improving the wet atomization level of the polypropylene composition.
In order to further improve the impact resistance of the polypropylene composition, the HDPE is preferably an HDPE with a melt mass flow rate of 0.2-10 g/10min at 190 ℃ under a load of 2.16 kg.
The excessive melt mass flow rate of HDPE means that the HDPE has small molecular weight, is easy to separate out, is unfavorable for anti-atomization performance, influences the notch impact strength of the simply supported beam of the material, and is unfavorable for molding production when the HDPE is too low.
The invention also specifically provides a preparation method of the anti-fogging polypropylene composition, which comprises the following steps:
s1, uniformly mixing polypropylene resin, a toughening agent, HDPE, a filler, an antioxidant, a light stabilizer and other additives to obtain a mixture;
s2, adding the mixture into a double-screw extruder, melting and mixing, wherein the mixing temperature is 170-220 ℃, the screw rotating speed is 350-450 rpm, and extruding and granulating to obtain the polypropylene composition.
The application of a polypropylene composition in the preparation of automotive interior parts is also within the scope of the invention.
The polypropylene composition has good wet atomization performance, greatly improves the condition that the polypropylene modified material of the automotive interior part emits small molecular substances and condenses on the automotive glass, and can be widely applied to the preparation of the automotive interior part.
An automotive interior part prepared from the polypropylene composition.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides an anti-fogging polypropylene composition, which is characterized in that a benzotriazole light stabilizer and/or a high molecular weight hindered amine light stabilizer and a phosphite antioxidant are added in a formula, so that the gloss retention rate of the material can reach more than 90 after a wet atomization test at 100 ℃ for 72 hours, the anti-fogging effect is excellent, the impact strength of a simply supported beam notch of the material can reach 42-53, the toughness is good, and the anti-fogging polypropylene composition can be widely applied to the preparation of automotive interior parts.
Drawings
FIG. 1 shows a glass plate after wet atomization of a polypropylene composition of a comparative example.
FIG. 2 shows a glass plate after wet atomization of the polypropylene composition of the present invention.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
Wherein, the raw material information for the examples of the present invention and the comparative examples is specifically described as follows:
polypropylene resin 1: performing bench production, wherein the MFR is 26g/10min, the atomization value is 90.6 under the conditions of 100 ℃ for 3 hours according to TSM0503G-2013 composite test B method amine composite method standard detection;
polypropylene resin 2: EP548R, produced by Mediterranean Shell, has an MFR of 26g/10min, measured according to TSM0503G-2013, composite test B amine composite standard, and an atomization value of 86 at 100 ℃ for 3 hours.
Polypropylene resin 3: the TPC is produced in Singapore, the MFR is 27g/10min, the atomization value is 96.6 under the conditions of 100 ℃ and 3 hours according to TSM0503G-2013 composite test B method amine composite method standard detection;
the toughening agent is an ethylene-butylene copolymer: ENGAGE7447, produced by DOW, USA, with MFR of 5g/10 min;
HDPE 1 is FL8008 produced by Fujian United petrochemical industry, and the MFR of the HDPE is 8g/10 min;
HDPE2 is HDPE2500 produced by SK in Korea, and its MFR is 0.2g/10 min;
HDPE 3 is HDPE6098 produced by medium petrochemical and ziphus petrochemical, and the MFR is 12g/10 min;
the talcum powder is produced by Liaoning Aihai talcum, the length-diameter ratio is 6:1, and the mesh number is 3000 meshes;
antioxidant 1010, a product produced by basf corporation, a hindered phenol antioxidant, having a relative molecular weight of 1178 and a melting point of 120 ℃;
antioxidant 686, a product produced by Tianjin Lianlong company, phosphite antioxidant with a relative molecular weight of 647 and a melting point of 185 ℃;
antioxidant 168, a product manufactured by basf corporation; phosphite ester antioxidant with relative molecular weight of 825 and melting point of 230 ℃;
antioxidant Rianox245, a product produced by Tianjin Lianlong company, phosphite ester antioxidant with the relative molecular weight of 587 and the melting point of 79 ℃;
the benzotriazole light stabilizer is as follows: UV-326, manufactured by Tianjin Lianlong company, melting point 140 ℃;
hindered amine light stabilizer: UV-770 with a relative molecular weight of 481, a melting point of 83 ℃ and manufactured by Tianjin Lianlong company;
hindered amine light stabilizer: LA-402AF, with a relative molecular weight of more than 1000, a melting point of 120 ℃ and manufactured by Addie;
hindered amine light stabilizer: LA-52, having a relative molecular weight of 847, a melting point of 65 ℃ and manufactured by Ediko;
benzophenone-based light stabilizer: UV531, relative molecular weight 326, melting point 50 ℃, manufactured by Tianjin Lianlong company;
the lubricant is calcium stearate, BS-3818 from Bailey chemical engineering (Zhongshan);
the specific test methods of the relevant properties of the examples and comparative examples of the present invention are as follows:
(1) MFR (melt flow Rate) determined according to ISO1133-2011, 230 ℃ C. 2.16kg
(2) Density is determined according to ISO1183-2019
(3) The tensile strength is tested by adopting a Zwick Z005 electronic universal tester according to ISO 527-2019;
(4) the impact strength of the notch of the simply supported beam is tested by adopting a Zwick HIT5.5P electronic display impact instrument according to ISO179-2010
(5) The bending strength and the bending modulus are tested according to ISO178-2019 by adopting a Zwick Z005 electronic universal tester;
(6) ordinary atomization, and testing by a glossiness method according to the conditions of TSM0503G-2013 and a compound test B method amine compound method of 100 ℃ for 3 hours;
(7) wet atomization, testing according to TSM0503G-2013 and compound test B method amine compound method 100 ℃ for 72 hours, glossiness method.
Example 1
An anti-fogging polypropylene composition comprises the following components in parts by weight as shown in the following table 1:
TABLE 1
Wherein, the preparation method of the polypropylene composition comprises the following steps:
s1, uniformly mixing all the components in proportion to obtain a mixture;
s2, adding the mixture into a double-screw extruder, melting and mixing, wherein the mixing temperature is 170-220 ℃, the screw rotating speed is 350-450 rpm, and extruding and granulating to obtain the polypropylene composition.
Comparative example 1
The polypropylene composition had the same composition and content as in example 1, except that 0.3 part of antioxidant 1010 was used.
Comparative example 2
A polypropylene composition having the same composition and content as in example 1, except that 0.3 part of UV531 as a light stabilizer was used.
Comparative example 3
The components and the content of the polypropylene composition are the same as those in example 1, except that the total content of phosphite antioxidant used is 0.7 part, and the specific proportion of the antioxidant 686 and the antioxidant 168 is the same as that in example 1.
Comparative example 4
The components and the content of the polypropylene composition are the same as those in example 1, except that the total content of phosphite antioxidant used is 0.08 part, and the specific content ratio of the antioxidant 686 to the antioxidant 168 is the same as that in example 1.
Comparative example 5
A polypropylene composition having the same composition and content as in example 1, except that the total content of the light stabilizers used was 0.6 part, wherein the content ratio of UV-326 to LA-402AF was the same as in example 1.
Comparative example 6
A polypropylene composition having the same composition and content as in example 1, except that the total content of the light stabilizers used was 0.08 parts, wherein the content ratio of UV-326 to LA-402AF was the same as in example 1.
Comparative example 7
A polypropylene composition having the same composition and content as in example 1, except that the amount of the filler used was 45 parts.
Comparative example 8
A polypropylene composition having the same composition and content as in example 1, except that 12 parts of HDPE was used.
Comparative example 9
The polypropylene composition had the same composition and content as in example 1, except that 25 parts of a toughening agent was used.
Comparative example 10
A polypropylene composition having the same composition and content as in example 1, except that the polypropylene used was EP 548R.
Result detection
Specific detection results are shown in tables 2 and 3 below
Table 2.
Table 3.
The performances of the related melt mass flow rate MFR, product density and rigidity (including tensile strength, bending strength and bending modulus) of the anti-fogging polypropylene composition are also detected, and all the performances can meet the related performance requirements, wherein the MFR of the anti-fogging polypropylene composition is 15-20 g/10min, and the density is 0.9-1.1 g/cm3The tensile strength is 15-18 MPa, the bending strength is 23-27 MPa, and the bending modulus is 1700-1780 MPa.
The wet atomization performance is improved without damaging the related performance.
As can be seen from Table 2, the wet atomization values of examples 1 to 14 were all greater than 90, and from Table 2, there was no correlation between the ordinary atomization and the wet atomization. The applicant of the invention can ensure that the gloss retention rate of the material can reach more than 90 after a wet atomization test at 100 ℃ for 72 hours by adding at least one of the benzotriazole light stabilizer and the high-molecular-weight hindered amine light stabilizer in the formula.
As can be seen from the comparative examples, the changes of the antioxidant and the light stabilizer bring unexpected effects on the fogging properties, and the good fogging resistance, especially the wet fogging resistance, cannot be achieved by using the antioxidant and the light stabilizer outside the scope of the present invention.
FIG. 1 shows a glass plate after wet atomization of the polypropylene composition of comparative example 1, which shows a significant wet atomization phenomenon, and the specific anti-atomization performance of the anti-atomization polypropylene composition of the present invention prepared into related products is shown in FIG. 2, which shows that the surface of the product has no atomization phenomenon of related volatile components and has good wet atomization performance.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. An anti-fogging polypropylene composition is characterized by comprising the following components in parts by weight:
50-100 parts of polypropylene resin, 0-22 parts of toughening agent, 0-10 parts of HDPE, 0-40 parts of filler, 0.1-0.6 part of antioxidant and 0.1-0.5 part of light stabilizer,
the antioxidant is phosphite ester antioxidant, the light stabilizer is phenytriazole light stabilizer and/or hindered amine light stabilizer with the relative molecular weight more than or equal to 400,
the polypropylene resin is detected according to TSM0503G-2013 composite test B-method amine composite method standard, and the atomization value is not less than 90 under the condition of 100 ℃ for 3 hours.
2. The anti-fogging polypropylene composition according to claim 1, wherein the composition comprises the following components in parts by weight:
60-80 parts of polypropylene resin, 10-15 parts of toughening agent, 5-8 parts of HDPE, 20-30 parts of filler, 0.2-0.5 part of antioxidant and 0.2-0.3 part of light stabilizer.
3. The anti-fogging polypropylene composition according to claim 1, wherein the antioxidant has a relative molecular weight of 600 to 1000 and a melting point of 185 to 230 ℃.
4. The anti-fogging polypropylene composition according to claim 3, wherein the antioxidant is a compound antioxidant consisting of an antioxidant 168 and an antioxidant 686, and the mass ratio of the antioxidant 168 to the antioxidant 686 is 1-2: 1.
5. The anti-fogging polypropylene composition according to claim 1, wherein the light stabilizer is a benzotriazole light stabilizer and/or a hindered amine light stabilizer having a relative molecular weight of 800 or more.
6. The anti-fogging polypropylene composition according to claim 5, wherein the melting point of the light stabilizer is 120 to 140 ℃.
7. The anti-fogging polypropylene composition according to claim 6, wherein the light stabilizer is a composite light stabilizer comprising a light stabilizer UV326 and a light stabilizer LA-402AF, and the mass ratio of the light stabilizer UV326 to the light stabilizer LA-402AF is 1-2: 1.
8. A method for preparing the anti-fogging polypropylene composition according to any one of claims 1 to 7, characterised by comprising the steps of:
s1, uniformly mixing polypropylene resin, a toughening agent, HDPE, a filler, an antioxidant, a light stabilizer and other additives to obtain a mixture;
s2, adding the mixture into a double-screw extruder, melting and mixing, wherein the mixing temperature is 170-220 ℃, the screw rotating speed is 350-450 rpm, and extruding and granulating to obtain the polypropylene composition.
9. Use of a polypropylene composition according to any one of claims 1 to 7 for the preparation of automotive interior parts.
10. An automotive interior part, characterized in that it is produced from the polypropylene composition according to any one of claims 1 to 7.
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| CN116041862A (en) * | 2022-12-29 | 2023-05-02 | 重庆普利特新材料有限公司 | High-performance low-condensation atomization modified polypropylene and preparation method thereof |
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