CN114685891A - PP/POE composition for gas-assisted molding and preparation method and application thereof - Google Patents
PP/POE composition for gas-assisted molding and preparation method and application thereof Download PDFInfo
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
- C08J9/105—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof containing sulfur
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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Abstract
The invention discloses a PP/POE composition for gas-assisted molding and a preparation method and application thereof. The PP/POE composition comprises the following components in parts by weight: 70-92 parts of PP resin, 5-20 parts of POE resin, 1-3 parts of chemical foaming agent, 0.5-1 part of scratch-resistant agent, 0.4-0.8 part of odor adsorbent and 0.6-3 parts of other auxiliary agent. The PP/POE composition has low density, low odor and excellent scratch resistance through the synergistic interaction of the scratch resistance agent, the odor adsorbent and the chemical foaming agent with the PP resin and the POE resin.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a PP/POE composition for gas-assisted molding and a preparation method and application thereof.
Background
Along with the development of automobile lightweight, automobile parts use plastic products more and more, through the fashioned part of gas-assisted, can effectual weight reduction, adapt to the requirement of automobile lightweight.
The gas-assisted molding process is characterized in that high-pressure inert gas is injected into molten plastic in the production process to form a vacuum section and push molten materials to advance, so that the processes of injection, pressure maintaining, cooling and the like are realized. The product produced by the method has the advantages of reducing the weight of the product, eliminating sink marks, improving the production efficiency, improving the degree of freedom of product design and the like,
as reported in the prior art, a filled polypropylene composition for gas-assisted molding and a preparation method thereof are used for producing an automobile door handle by using a filled polypropylene material for gas-assisted molding. The polypropylene is added with inorganic filler and nitrile rubber materials, so that the molding period is shortened, the material warping is reduced, and the polypropylene composite can be widely applied to gas-assisted molded products such as automobile door handles, window frame trim strips and the like.
However, the density of the polypropylene material for gas-assisted forming reported in the prior art is still high, and the weight of the product parts subjected to gas-assisted forming is large. The scratch resistance of the gas-assisted molded product material is poor, and after the part is scratched in the long-term use process, the surface of the part is obviously whitened, so that the appearance effect of the part in use is influenced. In addition, the process temperature of the gas-assisted molding is high, generally 230-240 ℃, and partial decomposition of materials exists in the preparation process, so that the product has a large smell.
Therefore, there is a need to develop a low density, low odor, scratch resistant PP/POE composition for gas assist molding.
Disclosure of Invention
The invention provides a PP/POE composition for gas-assisted molding, aiming at overcoming the defects of high density, strong smell and no scratch resistance in the prior art.
Another object of the present invention is to provide a process for preparing the above PP/POE composition.
Another object of the present invention is to provide the use of the PP/POE composition.
In order to solve the technical problems, the invention adopts the technical scheme that:
the PP/POE composition for gas-assisted molding comprises the following components in parts by weight:
70-92 parts of PP resin,
5-20 parts of POE resin,
1-3 parts of a chemical foaming agent,
0.5 to 1 part of scratch resistant agent,
0.4 to 0.8 part of odor adsorbent,
0.6-3 parts of other additives.
The POE resin is mixed with the PP resin in a small content, and the formed PP/POE resin matrix has better impact resistance and can reduce the density of the material. Chemical blowing agents further reduce the density of the material by forming dense closed cells within the material during extrusion of the PP/POE composition of the present invention.
The scratch resistant agent is blended with other components in a master batch form, and the scratch resistant agent can increase the lubricity of the PP/POE composition, so that the scratch resistance of the material is improved. And the scratch-resistant agent can also reduce the friction coefficient between the surface of the material and the surface of a die in the processing process, and reduce the appearance defects of the surface of a part. The inventor surprisingly finds out through creative experiments that the addition of the scratch-resistant agent obviously reduces the gas-assisted forming processing temperature of the material, reduces the decomposition of the material and further reduces the odor of the material.
On the basis of the scratch-resistant agent, the odor adsorbent can assist in absorbing part of odor generated by the material in the processing process, and further reduce the odor of the PP/POE composition.
The PP/POE composition has low density, low odor and excellent scratch resistance through the synergistic interaction of the scratch resistance agent, the odor adsorbent and the chemical foaming agent with the PP resin and the POE resin.
Preferably, the melt flow rate of the PP resin at 230 ℃ and 2.16kg is 8-30 g/10 min.
The POE resin is metallocene-catalyzed ethylene-octene copolymer or ethylene-butene copolymer.
Preferably, the melt flow rate of the POE resin at 190 ℃ under the condition of 2.16kg is 5-20 g/10 min.
The melt flow rate was measured according to ISO 1133-1-2011 standard method.
Preferably, the chemical foaming agent is one or more of tosylsemicarbazide, azodicarbonamide or 4, 4' -disulfonyl hydrazide diphenyl ether.
Preferably, the scratch resistant agent is an oleamide type scratch resistant agent and/or a silicone type scratch resistant agent.
More preferably, the scratch resistant agent is a silicone based scratch resistant agent.
Further preferably, the silicone-based scratch resistant agent is silicone master batch. The silicone master batch comprises silicone and carrier resin. Preferably, the carrier resin is polypropylene and/or polyethylene.
Preferably, the average pore size of the odor adsorbent is 40 to 60 μm.
Preferably, the odor adsorbent is one or more of diatomite, activated carbon or silica gel.
More preferably, the odor adsorbent is diatomaceous earth.
The other auxiliary agents are one or more of an antioxidant, a light stabilizer or a toner.
The antioxidant can be one or more of antioxidant 1010, antioxidant 168 or antioxidant BHT.
The light stabilizer may be a hindered amine light stabilizer and/or a hindered phenol light stabilizer.
The toner can be one or more of carbon black, phthalocyanine blue, phthalocyanine green or titanium dioxide.
The invention also provides a preparation method of the PP/POE composition, which comprises the following steps:
mixing PP resin, POE resin, a chemical foaming agent, a scratch-resistant agent, an odor adsorbent and other auxiliaries, adding the mixture into an extruder, and performing melt mixing, extrusion and granulation to obtain the PP/POE composition.
Preferably, the extruder is a twin screw extruder.
More preferably, the extrusion temperature of the double-screw extruder is 210-230 ℃, the screw rotating speed is 450-550 rpm, and the feeding speed is 600-800 kg/h.
The invention also protects the application of the PP/POE composition in preparing gas-assisted molded products.
Optionally, the gas-assisted molded article is an automobile inner door handle, an automobile tail door guard plate, a door panel decorating part, an automobile elbow or the like.
Preferably, the gas-assisted forming temperature of the gas-assisted forming product is 210-220 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the invention develops a PP/POE composition for gas-assisted molding, which has low density, low odor and scratch resistance. The PP/POE composition has low density, low odor and excellent scratch resistance through the synergistic interaction of the scratch resistance agent, the odor adsorbent and the chemical foaming agent with the PP resin and the POE resin.
Detailed Description
The present invention will be further described with reference to the following embodiments.
The raw materials in the examples and comparative examples are all commercially available;
the reagents, methods and apparatus employed in the present invention are conventional in the art, except as otherwise indicated.
Examples 1 to 12
Examples 1 to 12 respectively provide a PP/POE composition, the component contents of which are shown in table 1, and the preparation method is as follows:
mixing the components according to the table 1, adding the mixture into a double-screw extruder, and performing melt mixing, extrusion and granulation to obtain a PP/POE composition; wherein the extrusion temperature of the double-screw extruder is 210-230 ℃, the screw rotating speed is 450-550 rpm, and the feeding speed is 600-800 kg/h.
TABLE 1 component contents (parts by weight) of PP/POE compositions of examples 1 to 12
Comparative examples 1 to 5
Comparative examples 1 to 5 respectively provide a PP/POE composition, the component contents of which are shown in Table 2, and the preparation method comprises the following steps:
mixing the components according to the table 2, adding the mixture into a double-screw extruder, and performing melt mixing, extrusion and granulation to obtain a PP/POE composition; wherein the extrusion temperature of the double-screw extruder is 210-230 ℃, the screw rotating speed is 450-550 rpm, and the feeding speed is 600-800 kg/h.
TABLE 2 component contents (parts by weight) of PP/POE compositions of comparative examples 1 to 5
| 1 | 2 | 3 | 4 | 5 | ||
| PP resin | PP-1 | 80 | 80 | 80 | 80 | 80 |
| POE resin | POE-1 | 10 | 10 | 10 | - | 10 |
| Chemical foaming agent | Tosylsemicarbazides | - | 2 | 2 | 2 | 2 |
| Scratch-resistant agent | Oleic acid amides | 0.8 | - | 0.8 | 0.8 | 1.5 |
| Odor adsorbent | Diatomaceous earth-1 | 0.6 | 0.6 | - | 0.6 | 0.6 |
Performance testing
The PP/POE compositions prepared in the above examples and comparative examples were tested for their performance by the following specific methods:
density: testing by using a densitometer according to method A in GB 1033-1-2008;
odor: preparing an automobile door handle-shaped product from the PP/POE composition in an air-assisted molding manner, and testing according to a PV3900-2019 testing method, wherein the weight of a tested material is 20g, the baking temperature of the material is 80 ℃, and the baking time is 2 hours; wherein the PP/POE compositions of examples 1-12 and comparative examples 1, 3 and 4 have an air-assisted forming temperature of 210-220 ℃, and the PP/POE composition of comparative example 2 has an air-assisted forming temperature of 230-240 ℃;
scratch resistance: the test was carried out according to the method of QJ/GAC 1550.004-2019, wherein the doctor blade is a hard metal spherical blade tip with a diameter of 1mm, the test load F is 10N, and the color difference DeltaL before and after scratching is measured.
The test results of the examples and comparative examples are shown in Table 3.
TABLE 3 test results of examples and comparative examples
From the test results in table 3, the PP/POE compositions prepared in the examples of the present invention all had low density, low odor, and excellent scratch resistance. The PP/POE compositions of examples 1 to 12 had densities of 0.68g/cm or less3The odor grade after air-assisted molding is below 4 gradeAnd (4) performing scratch test, wherein the color difference Delta L of the surface of the material is less than or equal to 0.7.
The density of the PP resin is reduced to a certain extent by introducing the POE resin, and meanwhile, the density of the material is further reduced by forming compact closed pores in the material by the chemical foaming agent. The scratch resistance of the PP/POE composition is improved and the odor degree of the PP/POE composition is greatly reduced due to the addition of the scratch resistance agent.
According to the embodiments 1 to 5, when the melt flow rate of the POE resin at 190 ℃ under the condition of 2.16kg is 5 to 20g/10min, and the melt flow rate of the PP resin at 230 ℃ under the condition of 2.16kg is 8 to 30g/10min, the PP/POE composition has better synergistic effect of the components, lower odor and better scratch resistance.
From the examples 1 and 8-10, it can be seen that when the odor adsorbent is diatomite, the prepared PP/POE composition has a smaller odor grade; and the diatomite and the scratch resistant agent have better synergistic effect, so that the PP/POE composition has better scratch resistant performance.
The PP/POE composition of comparative example 1 contained no blowing agent; in comparative example 4, POE was not contained. The PP/POE compositions obtained in comparative examples 1 and 4 have a higher density. And in comparative example 1, the odor emission is more serious because closed pores cannot be formed inside the material to lock the odor small molecular substance.
The comparative example 2 does not contain a scratch resistant agent, so that the prepared PP/POE composition has poor scratch resistant performance, the PP/POE composition is difficult to be subjected to gas-assisted molding at 210-220 ℃, and the gas-assisted molding can be realized only at a higher temperature (230-240 ℃). At too high a temperature, partial degradation of the material occurs, resulting in an excessive odor.
In comparative example 3, without the odor adsorbent, the resulting PP/POE composition had an odor rating of too high.
In comparative example 5, the scratch resistance agent is too much, which causes the reduction of the melt strength of the material, resulting in the rupture of foamed cells, the foaming effect is poor, the density of the PP/POE composition is too high, and the scratch resistance agent is too much to affect the odor, and the odor grade of the PP/POE composition is 5.5.
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. The PP/POE composition for gas-assisted molding is characterized by comprising the following components in parts by weight:
70-92 parts of PP resin,
5-20 parts of POE resin,
1-3 parts of a chemical foaming agent,
0.5 to 1 part of scratch resistant agent,
0.4 to 0.8 part of odor adsorbent,
0.6-3 parts of other additives.
2. The PP/POE composition of claim 1, wherein the PP resin has a melt flow rate of 8-30 g/10min at 230 ℃ and 2.16 kg.
3. The PP/POE composition of claim 1, wherein the POE resin has a melt flow rate of 5-20 g/10min at 190 ℃ and 2.16 kg.
4. The PP/POE composition of claim 1, wherein the chemical blowing agent is one or more of tosylsemicarbazide, azodicarbonamide, or 4, 4' -disulfonylhydrazide diphenyl ether.
5. The PP/POE composition of claim 1, wherein the scratch resistance agent is an oleamide type scratch resistance agent and/or a silicone type scratch resistance agent.
6. The PP/POE composition of claim 1, wherein the odor adsorbent is one or more of diatomaceous earth, activated carbon, or silica gel.
7. The PP/POE composition of claim 1, wherein the other auxiliary agents are one or more of antioxidants, light stabilizers or toner.
8. A method for preparing the PP/POE composition of any one of claims 1 to 7, comprising the steps of:
mixing PP resin, POE resin, a chemical foaming agent, a scratch-resistant agent, an odor adsorbent and other auxiliaries, adding the mixture into an extruder, and performing melt mixing, extrusion and granulation to obtain the PP/POE composition.
9. Use of the PP/POE composition of any one of claims 1 to 7 in the preparation of gas-assisted molded articles.
10. The use according to claim 9, wherein the gas-assisted forming temperature of the gas-assisted formed article is 210 to 220 ℃.
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