CN113321866A - Laser direct forming polypropylene material and preparation method thereof - Google Patents
Laser direct forming polypropylene material and preparation method thereof Download PDFInfo
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- CN113321866A CN113321866A CN202010128582.7A CN202010128582A CN113321866A CN 113321866 A CN113321866 A CN 113321866A CN 202010128582 A CN202010128582 A CN 202010128582A CN 113321866 A CN113321866 A CN 113321866A
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- 239000000463 material Substances 0.000 title claims abstract description 58
- -1 polypropylene Polymers 0.000 title claims abstract description 55
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 47
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims abstract description 24
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 20
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 20
- 239000000654 additive Substances 0.000 claims abstract description 19
- 230000000996 additive effect Effects 0.000 claims abstract description 17
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 12
- 239000000440 bentonite Substances 0.000 claims abstract description 12
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012745 toughening agent Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000001125 extrusion Methods 0.000 claims description 18
- 239000008187 granular material Substances 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 6
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical group CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 abstract description 11
- 239000006185 dispersion Substances 0.000 abstract description 4
- 239000012752 auxiliary agent Substances 0.000 abstract 4
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 abstract 2
- 238000005054 agglomeration Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 238000004062 sedimentation Methods 0.000 abstract 1
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a laser direct forming polypropylene material and a preparation method thereof, wherein the laser direct forming polypropylene material comprises the following components in parts by mass: 50-75 parts of polypropylene, 5 parts of LDS additive, 5-10 parts of nano organic bentonite, 10-20 parts of ethylene-vinyl alcohol copolymer, 2-6 parts of propylene carbonate, 4-8 parts of toughening agent and 0.5 part of antioxidant. According to the invention, the LDS auxiliary agent is added into the polypropylene material through a blending-based process, and compared with the traditional base material LDS material, the LDS auxiliary agent has the advantages of lower cost and higher creep resistance. The addition of EVOH converts the material from non-polarity to a surface with high hydrophilic performance, the dispersion system of the nano organobentonite composite propylene carbonate can effectively prevent the sedimentation and agglomeration of the LDS auxiliary agent, the rigidity of the material is improved to a certain extent, and the addition of the toughening agent compensates for the toughness reduction caused by the addition of the LDS auxiliary agent and the high-crystalline EVOH material.
Description
Technical Field
The invention relates to the field of functional materials, in particular to a laser direct forming polypropylene material and a preparation method thereof.
Background
Laser Direct Structuring (LDS), a laser process-based production technology, uses laser to directly transfer a circuit pattern to the surface of a molded object, forming a circuit structure on the three-dimensional surface of a three-dimensional workpiece. The use of the technology reduces the weight and the volume of the product and increases the design freedom of the product. Based on these advantages, LDS materials have been applied to the fields of medical devices, communication equipment, electronic circuits for automobiles, and the like. The LDS technology has high requirements for the basic polypropylene material used therein, and not only needs good melt flowability, but also needs high mechanical strength, fast molding cycle and dimensional stability. At present, matrix resins applied to laser direct forming materials are generally engineering plastics with higher polarity, such as PC, PBT, PA and the like, which are generally poor in water resistance and high in processing difficulty and are not suitable for preparing products with larger quantities.
The polypropylene is the most widely used thermoplastic material except polyethylene in the current general plastic, and has simple forming and low price. However, in the field of laser direct structuring materials, since the LDS process has a chemical plating process, and the very low surface polarity of polypropylene causes very poor affinity between the material and water, which affects the efficiency of laser direct structuring, it has not been widely developed at present.
Disclosure of Invention
The invention aims to provide a laser direct forming polypropylene material and a preparation method thereof, which aim to solve the problems in the prior art.
The purpose of the invention is realized by the following technical scheme:
a laser direct forming polypropylene material comprises the following components in parts by mass:
in a further scheme, the melt index of the polypropylene is more than or equal to 26g/10min under the condition of 230 ℃/2.16kg, the shrinkage rate is 1.4-1.6%, and the notch impact strength is more than or equal to 90J/m.
Further, the LDS additive is at least one of Iriotec8841, Iriotec8842, and Iriotec 8850.
In a further scheme, the relative density of the organic bentonite is 1.7-1.8g/cm3(ii) a The ethylene-vinyl alcohol copolymer has an ethylene content of 25-35%.
In a further scheme, the toughening agent is an ethylene-propylene copolymer, an ethylene-octene copolymer or an ethylene-butene copolymer.
In a further scheme, the antioxidant is at least one of hindered phenol antioxidant and phosphite antioxidant; more preferably, the hindered phenol antioxidant is n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and the phosphite antioxidant is tris- (2, 4-di-tert-butylphenyl) phosphite.
According to a further scheme, the antioxidant is prepared from hindered phenol antioxidant and phosphite antioxidant according to a mass ratio of 1: 1.
The invention also aims to provide a preparation method of the laser direct structuring polypropylene material, which comprises the following steps:
(1) adding 50-75 parts of polypropylene, 5 parts of LDS additive, 5-10 parts of nano organic bentonite, 10-20 parts of ethylene-vinyl alcohol copolymer, 2-6 parts of propylene carbonate, 4-8 parts of toughening agent and 0.5 part of antioxidant into a high-speed mixer, and mixing at high speed to obtain a mixed material;
(2) and (2) adding the mixed material obtained in the step (1) into a double-screw extruder, mixing, extruding, cooling and granulating to obtain the laser direct-forming polypropylene granules.
Further, the extrusion temperature of each extrusion zone in the twin-screw extruder is respectively 170-
Compared with the prior art, the invention has the beneficial effects that:
(1) the laser direct forming polypropylene material provided by the invention adds the LDS additive into the polypropylene material through a blending-based process. Compared with the traditional substrate LDS material, the cost is lower.
(2) The invention improves the polarity of the material by adding the ethylene-vinyl alcohol copolymer (EVOH), so that the material is changed from non-polar to highly hydrophilic.
(3) The intercalation of the nano organobentonite can play a physical isolation effect on the LDS additive, and the high dispersibility of the propylene carbonate is combined, so that the dispersion system can effectively prevent the LDS additive from settling and agglomerating, and meanwhile, the rigidity of the material is improved to a certain extent.
(4) According to the invention, the defect that the toughness of the material is reduced due to the addition of the LDS additive and the EVOH is overcome by adding the toughening agent, so that the prepared material has good polarity and toughness.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The types and suppliers of reagents used in this example were as follows:
the polypropylene is available from China Korean petrochemical Wuhan factory under the trademark PP-K7227H;
the LDS additives are commercially available LDS additives available from Merck chemistry under the designations including, but not limited to, Iriotec8841, Iriotec8842, and Iriotec 8850.
The reagents are provided only for illustrating the sources and components of the reagents used in the experiments of the present invention, so as to be fully disclosed, and do not indicate that the present invention cannot be realized by using other reagents of the same type or other reagents supplied by other suppliers.
Example 1
50 parts of polypropylene material, 5 parts of Iriotec8841 additive, 10 parts of nano organic bentonite, 20 parts of ethylene-vinyl alcohol copolymer (EVOH), 6 parts of propylene carbonate, 8 parts of ethylene-octene copolymer and 0.5 part of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate are added into a high-speed mixer to be mixed for 5min, and then the uniformly mixed materials are added into a double-screw extruder to be mixed, extruded, cooled and cut into granules, thus obtaining the laser direct forming polypropylene granules. Wherein the extrusion temperatures of the extrusion zones in the twin-screw extruder are 180 ℃, 190 ℃, 200 ℃, 210 ℃ respectively. The properties of the obtained product are shown in Table 1.
Example 2
65 parts of polypropylene material, 5 parts of Iriotec8841 additive, 8 parts of nano organic bentonite, 15 parts of ethylene-vinyl alcohol copolymer (EVOH), 4 parts of propylene carbonate, 6 parts of ethylene-octene copolymer and 0.5 part of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate are added into a high-speed mixer to be mixed for 5min, and then the uniformly mixed materials are added into a double-screw extruder to be mixed, extruded, cooled and cut into granules to obtain the laser direct forming polypropylene granules. Wherein the extrusion temperatures of the extrusion zones in the twin-screw extruder are 175 ℃, 185 ℃, 195 ℃, 205 ℃ respectively. The properties of the obtained product are shown in Table 1.
Example 3
75 parts of polypropylene material, 5 parts of Iriotec8841 additive, 5 parts of nano organic bentonite, 10 parts of ethylene-vinyl alcohol copolymer (EVOH), 2 parts of propylene carbonate, 4 parts of ethylene-octene copolymer and 0.5 part of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate are added into a high-speed mixer to be mixed for 5min, and then the uniformly mixed materials are added into a double-screw extruder to be mixed, extruded, cooled and cut into granules, thus obtaining the laser direct forming polypropylene granules. Wherein the extrusion temperatures of the extrusion zones in the double-screw extruder are respectively 170 ℃, 180 ℃, 190 ℃ and 200 ℃. The properties of the obtained product are shown in Table 1.
Example 4
65 parts of polypropylene material, 5 parts of Iriotec8841 additive, 8 parts of nano organic bentonite, 15 parts of ethylene-vinyl alcohol copolymer (EVOH), 4 parts of propylene carbonate, 6 parts of ethylene-octene copolymer, 0.25 part of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate and 0.25 part of tri- (2, 4-di-tert-butylphenyl) phosphite are added into a high-speed mixer to be mixed for 5min, and then the uniformly mixed materials are added into a double-screw extruder to be mixed, extruded and cooled and cut into granules to obtain the laser directly-molded polypropylene granules. Wherein the extrusion temperatures of the extrusion zones in the twin-screw extruder are 175 ℃, 185 ℃, 195 ℃, 205 ℃ respectively. The properties of the obtained product are shown in Table 1.
Table 1 results of property measurements of materials prepared in examples 1 to 3
Note: the conditions for the above test and the dimensions of the test bars are as follows:
notched izod impact strength: model a, molding notches, sample size 100mm by 10mm by 4 mm;
flexural modulus: sample size 100mm 10mm 4 mm;
contact angle test: sample size 360mm 100mm 3 mm.
Comparative example 1
70 parts of polypropylene material, 5 parts of Iriotec8841 additive, 10 parts of nano organic bentonite, 6 parts of propylene carbonate, 8 parts of ethylene-octene copolymer and 0.5 part of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate are added into a high-speed mixer to be mixed for 5min at high speed, and then the uniformly mixed materials are added into a double-screw extruder to be mixed, extruded, cooled and cut into granules to obtain the laser direct forming polypropylene granules. Wherein the extrusion temperatures of the extrusion zones in the twin-screw extruder are 180 ℃, 190 ℃, 200 ℃, 210 ℃ respectively. The properties of the obtained product are shown in Table 2.
Comparative example 2
65 parts of polypropylene material, 5 parts of Iriotec8841 additive, 20 parts of ethylene-vinyl alcohol copolymer (EVOH), 8 parts of ethylene-octene copolymer and 0.5 part of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate are added into a high-speed mixer to be mixed for 5min at high speed, and then the uniformly mixed materials are added into a double-screw extruder to be mixed and extruded, cooled and granulated to obtain the laser direct forming polypropylene granules. Wherein the extrusion temperatures of the extrusion zones in the twin-screw extruder are 180 ℃, 190 ℃, 200 ℃, 210 ℃ respectively. The product properties are shown in Table 2.
Comparative example 3
58 parts of polypropylene material, 5 parts of Iriotec8841 additive, 10 parts of nano organic bentonite, 20 parts of ethylene-vinyl alcohol copolymer (EVOH), 6 parts of propylene carbonate and 0.5 part of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate are added into a high-speed mixer to be mixed for 5min at high speed, and then the uniformly mixed materials are added into a double-screw extruder to be mixed, extruded, cooled and cut into granules to obtain the laser direct forming polypropylene granules. Wherein the extrusion temperatures of the extrusion zones in the twin-screw extruder are 180 ℃, 190 ℃, 200 ℃, 210 ℃ respectively. The product properties are shown in Table 2.
TABLE 2 results of testing the properties of the materials prepared in comparative examples 1-3
It can be seen from the implementation case and the comparison case that the hydrophilicity of the material is greatly improved by adding EVOH, the dispersion uniformity of the filler is ensured by adding the dispersion system compounded by the nano organobentonite and the propylene carbonate, and the overall mechanical property of the material is improved.
The embodiments described above are intended to facilitate one of ordinary skill in the art in understanding and using the present invention. 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 embodiments described herein, 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 (10)
1. A laser direct structuring polypropylene material, characterized in that: the composition comprises the following components in parts by mass:
50-75 Parts of Polypropylene (PP),
5 parts of an LDS additive agent, namely,
5-10 parts of nano organic bentonite,
10-20 parts of ethylene-vinyl alcohol copolymer,
2-6 parts of propylene carbonate,
4-8 parts of a toughening agent,
0.5 part of antioxidant.
2. The laser direct structuring polypropylene material of claim 1, wherein: the melt index of the polypropylene under the condition of 230 ℃/2.16kg is more than or equal to 26g/10min, the shrinkage rate is 1.4-1.6%, and the notch impact strength is more than or equal to 90J/m.
3. The laser direct structuring polypropylene material of claim 1, wherein: the LDS additive is at least one of Iriotec8841, Iriotec8842 and Iriotec 8850.
4. The laser direct structuring polypropylene material of claim 1, wherein: the relative density of the organic bentonite is 1.7-1.8g/cm3(ii) a What is needed isThe ethylene-vinyl alcohol copolymer has an ethylene content of 25 to 35%.
5. The laser direct structuring polypropylene material of claim 1, wherein: the toughening agent is an ethylene-propylene copolymer, an ethylene-octene copolymer or an ethylene-butene copolymer.
6. The laser direct structuring polypropylene material of claim 1, wherein: the antioxidant is at least one of hindered phenol antioxidant and phosphite antioxidant.
7. The laser direct structuring polypropylene material of claim 6, wherein: the hindered phenol antioxidant is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate, and the phosphite antioxidant is tris- (2, 4-di-tert-butylphenyl) phosphite.
8. The laser direct structuring polypropylene material of claim 6, wherein: the antioxidant is prepared from hindered phenol antioxidant and phosphite antioxidant according to a mass ratio of 1: 1.
9. The process for preparing a laser direct structuring polypropylene material according to any one of claims 1 to 8, wherein: the method comprises the following steps:
(1) adding 50-75 parts of polypropylene, 5 parts of LDS additive, 5-10 parts of nano organic bentonite, 10-20 parts of ethylene-vinyl alcohol copolymer, 2-6 parts of propylene carbonate, 4-8 parts of toughening agent and 0.5 part of antioxidant into a high-speed mixer, and mixing at high speed to obtain a mixed material;
(2) and (2) adding the mixed material obtained in the step (1) into a double-screw extruder, mixing, extruding, cooling and granulating to obtain the laser direct-forming polypropylene granules.
10. The method of claim 9, wherein: the extrusion temperature of each extrusion zone in the double-screw extruder is respectively 170-.
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| CN115772295A (en) * | 2022-11-25 | 2023-03-10 | 无锡赢同新材料科技有限公司 | Low-specific-gravity laser direct forming material and preparation method and application thereof |
| CN116144102A (en) * | 2021-11-19 | 2023-05-23 | 广东中塑新材料有限公司 | High-toughness polypropylene material and preparation method thereof |
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