CN114292364A - Silane grafted polypropylene, crosslinked polypropylene material and preparation method thereof - Google Patents
Silane grafted polypropylene, crosslinked polypropylene material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a silane grafted polypropylene, a crosslinked polypropylene material and a preparation method thereof, belonging to the technical field of polypropylene materials. The silane grafted polypropylene comprises the following components in parts by mass: 100 parts of polypropylene, 1-8 parts of degradation inhibitor, 1.5-4.5 parts of silane grafting agent, 0.01-0.2 part of initiator and 0.001-0.01 part of auxiliary crosslinking agent; according to the invention, the initiator, the auxiliary crosslinking agent and the degradation inhibitor are selected and matched with polypropylene for silane grafting, so that silane grafted polypropylene can be obtained; the cross-linked polypropylene material is further used as a material A of the cross-linked polypropylene material and is mixed with a material B consisting of 100 parts of polypropylene, 5-20 parts of antioxidant and 0.01-0.05 part of stabilizer to prepare the cross-linked polypropylene material with excellent mechanical property and heat resistance; meanwhile, the preparation method provided by the invention is simple, easy to operate and beneficial to mass production.
Description
Technical Field
The invention belongs to the technical field of polypropylene materials, and particularly relates to a silane grafted polypropylene, a crosslinked polypropylene material and a preparation method thereof.
Background
The polypropylene (PP) has excellent performance and low cost, is the second most common plastic material in polyolefin plastics, which is second to the Polyethylene (PE), and is widely applied to the fields of daily necessities, building profiles, pipelines, fibers, films and the like; the rigidity of PP is obviously superior to that of other polyolefin materials, and the PP has great advantage over the cost of engineering plastics, so that the PP material applied to the aspect of stress support occupies a large market (for example, the automobile bumper material is basically modified PP or steel); but the heat distortion temperature of PP is lower, the mechanical property is not good at high temperature, and the application of PP material in some high-end fields is limited (for example, peripheral materials of automobile engines are mostly nylon, and corrosion-resistant and high-temperature-resistant industrial pipelines are mostly glass fiber reinforced plastics); therefore, the PP material is modified, and great economic benefits are achieved.
Researches on PP modification have been carried out for a long time, and physical modification such as glass fiber filled PP, basalt fiber reinforced PP and the like is generally applied, but most of the physical modification can improve the normal-temperature mechanical property, and the defect of insufficient heat resistance of PP cannot be solved all the time.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a silane grafted polypropylene and crosslinked polypropylene material with excellent heat resistance and mechanical property and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: the silane grafted polypropylene comprises the following components in parts by mass: 100 parts of polypropylene, 1-8 parts of degradation inhibitor, 1.5-4.5 parts of silane grafting agent, 0.01-0.2 part of initiator and 0.001-0.01 part of auxiliary crosslinking agent.
According to the invention, the initiator, the auxiliary crosslinking agent and the degradation inhibitor are selected to be matched with polypropylene for silane grafting to obtain silane grafted polypropylene, and further, the silane grafted polypropylene is used as a raw material to prepare the crosslinked polypropylene material which has higher crosslinking degree, so that good heat resistance and excellent mechanical property are embodied.
As a preferred embodiment of the silane grafted polypropylene, the silane grafted polypropylene comprises the following components in parts by mass: 100 parts of polypropylene, 1.5-7.5 parts of degradation inhibitor, 2.5-4.5 parts of silane grafting agent, 0.01-0.02 part of initiator and 0.001-0.002 part of assistant crosslinking agent.
When the components of the silane grafted polypropylene are in the range, the cross-linked polypropylene material prepared by using the silane grafted polypropylene as the raw material has higher gel fraction and better mechanical property and heat resistance, wherein the gel fraction is more than 43%, the yield strength is more than 38.9MPa, and the heat deformation temperature is more than 128.2 ℃.
As a preferred embodiment of the silane-grafted polypropylene of the present invention, the melt index of the polypropylene is 3 to 20 g/min.
The melt index of the polypropylene is preferably in the range, so that the difficulty in extrusion granulation caused by too low melt index can be avoided, and the insufficient mechanical property of the material prepared subsequently caused by too high melt index can be avoided.
As a preferred embodiment of the silane-grafted polypropylene of the present invention, the degradation inhibitor comprises dithiocarbamate, and dithiocarbamate.
The side methyl group of the polypropylene has influence on the main chain, so that oxidative degradation reaction can easily occur in the process of adding an initiator and a grafting agent for grafting modification, thereby causing low grafting efficiency and difficult crosslinking, therefore, a degradation inhibitor is added in the formula, the degradation in the grafting process can be effectively avoided, the grafting efficiency is improved, and the crosslinking degree is increased; dithiocarbamate species are preferred as degradation inhibitors because the removal of the formed radicals from the dithiocarbamate is more stable than the polypropylene macromolecular radicals, and the presence of the dithiocarbamate reduces chain scission of the polypropylene due to the formation of dormant species.
As a preferred embodiment of the silane-grafted polypropylene of the present invention, the degradation inhibitor comprises zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate or zinc dibutyldithiocarbamate.
As a preferred embodiment of the silane-grafted polypropylene of the present invention, the degradation inhibitor comprises zinc dimethyldithiocarbamate.
The reason why zinc dithiocarbamate is further preferred as a degradation inhibitor rather than dithiocarbamate is that dithiocarbamate has a slower rate of forming radicals and forms a smaller amount of radicals during the crosslinking reaction, so that the effect of avoiding degradation is inferior to that of zinc dithiocarbamate, and sodium dithiocarbamate is not selected because zinc has a higher electronegativity than sodium, and the formed salts thereof form more stable radicals which are then formed, and can act continuously without radical reduction, thereby ensuring that the chain is broken as little as possible; zinc dimethyldithiocarbamate is preferred because the side chain of the free radical formed is dimethyl, which is smaller and more stable in molecular weight, and therefore, reduces chain scission to a greater extent.
As a preferred embodiment of the silane-grafted polypropylene of the present invention, the silane grafting agent comprises trimethoxysilanes.
As a preferred embodiment of the silane-grafted polypropylene of the present invention, the silane grafting agent comprises 3- (methacryloyl) propyltrimethoxysilane, vinyltrimethoxysilane, 3-aminopropyltrimethoxysilane or methylpropyloxypropyltrimethoxysilane.
As a preferred embodiment of the silane-grafted polypropylene of the present invention, the silane grafting agent is 3- (methacryloyl) propyltrimethoxysilane.
Trimethoxysilanes are preferred as grafting agents, especially 3- (methacryloyl) propyltrimethoxy silane, because the grafting reaction activity is high, the grafting efficiency is high, and the heat resistance of the prepared silane-grafted polypropylene is better.
As a preferred embodiment of the silane-grafted polypropylene of the present invention, the initiator comprises trioxepanes.
As a preferred embodiment of the silane-grafted polypropylene of the present invention, the initiator comprises 3,3,5,7,7, -pentamethyl-1, 2, 4-trioxepane.
The trioxoheptane substance, particularly 3,3,5,7,7, -pentamethyl-1, 2, 4-trioxepane, is preferably used as an initiator, and the decomposition temperature is considered to be higher, so that the trioxoheptane substance can be well matched with the molten state of a polypropylene melt in the subsequent extrusion granulation preparation process, the grafting reaction of the polypropylene without fully homogenizing and mixing in the extrusion granulation process is avoided, and in addition, the degradation can be reduced to a certain extent due to the higher decomposition temperature.
As a preferred embodiment of the silane-grafted polypropylene of the present invention, the auxiliary crosslinking agent comprises a styrenic substance.
As a preferred embodiment of the silane-grafted polypropylene of the present invention, the co-crosslinking agent comprises styrene.
Styrene substances, particularly styrene, are preferably used as the auxiliary crosslinking agent, since the addition of styrene can improve the crosslinking density, the higher the crosslinking density is, the higher the strength of the crosslinked polypropylene material prepared in the later stage is, and the better the mechanical properties are.
In addition, the invention also provides a preparation method of the silane grafted polypropylene, which comprises the following steps: the components of the silane grafted polypropylene are uniformly mixed, extruded, granulated and dried to obtain the silane grafted polypropylene.
As a preferred embodiment of the preparation method of the silane-grafted polypropylene, the extrusion granulation is carried out in a parallel co-rotating twin-screw reaction extruder, and the temperature of the reaction extrusion granulation is 120-230 ℃.
In addition, the invention also provides a cross-linked polypropylene material, which comprises a material A and a material B; the material A is the silane grafted polypropylene; the material B comprises the following components in parts by mass: 100 parts of polypropylene, 5-20 parts of antioxidant and 0.01-0.05 part of catalyst.
The silane grafted polypropylene provided by the invention is selected as a material A of a cross-linked polypropylene material, and is matched with a material B for extrusion granulation or injection molding, so that the obtained material has excellent heat resistance and good mechanical properties.
As a preferred embodiment of the cross-linked polypropylene material of the present invention, the polypropylene is the same as the polypropylene in the material A.
As a preferred embodiment of the cross-linked polypropylene material of the present invention, the catalyst comprises an organotin species.
As a preferred embodiment of the crosslinked polypropylene material of the present invention, the catalyst comprises dibutyltin dilaurate.
As a preferred embodiment of the cross-linked polypropylene material, the mass ratio of the material A to the material B is (92-96): (4-8).
In addition, the invention also provides a preparation method of the cross-linked polypropylene material, which comprises the following steps: uniformly mixing the material A and the material B, and carrying out crosslinking reaction after extrusion or injection molding to obtain a crosslinked polypropylene material; the crosslinking reaction is carried out by soaking in water at 70-100 ℃ or steaming for 16-32 h.
Compared with the prior art, the invention has the beneficial effects that:
firstly, the method comprises the following steps: the technical scheme provided by the invention provides silane grafted polypropylene which can be applied to the preparation of a cross-linked polypropylene material, and the cross-linked polypropylene prepared by using the silane grafted polypropylene provided by the invention as a raw material has excellent heat resistance and mechanical properties;
secondly, the method comprises the following steps: the preparation method of the silane grafted polypropylene and crosslinked polypropylene material provided by the technical scheme of the invention is simple and convenient to operate, and can be applied to industrial production.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the invention will be further described with reference to specific examples, wherein the starting materials are commercially available in the usual manner unless otherwise indicated.
Example 1
The crosslinked polypropylene material of the embodiment comprises a material A and a material B, wherein the material A comprises the following components in parts by mass: 100 parts of polypropylene (HP 551M; melt index 9.5g/10 min; Liaoning Huajin chemical group Co., Ltd.), 1.5 parts of zinc dimethyldithiocarbamate (Liaoning Sanshi science and technology Co., Ltd.), 3 parts of 3- (methacryloyl) propyl trimethoxy silane (Dookangning Shanghai Co., Ltd.), 0.02 part of 3,3,5,7,7, -pentamethyl-1, 2, 4-trioxepane and 0.002 part of styrene; the material B comprises the following components in parts by mass: 100 parts of polypropylene, 20 parts of antioxidant 1010 (Shanghai tail chemical Co., Ltd.) and 0.03 part of dibutyltin dilaurate; wherein the mass ratio of the material A to the material B is 95: 5;
the preparation method specifically comprises the following steps:
(1) preparation of material A: weighing the components of the material A according to the weight parts, uniformly mixing, and performing reaction extrusion granulation and drying at the temperature of 120-230 ℃ by a Kedoulong STS96 parallel co-rotating twin-screw reaction extruder to obtain the material A;
(2) preparation of material B: weighing the components of the material B in parts by weight, uniformly mixing, extruding, granulating and drying at the temperature of 120-230 ℃ by a Kefenlong CTE65 parallel co-rotating twin-screw extruder to obtain a material B;
(3) uniformly mixing the material A and the material B according to the mass ratio, extruding, granulating and drying at the temperature of 160-200 ℃, and then putting into water at 95 ℃ for boiling for 8 hours to obtain the cross-linked polypropylene material.
Example 2
The difference between the present embodiment and embodiment 1 is that the formulation of the A, B material is different, and the material a of the present embodiment includes the following components in parts by mass: 100 parts of polypropylene (melt index: 9.5g/10min), 1.5 parts of sodium diethyldithiocarbamate, 3- (methacryloyl) propyltrimethoxysilane, 3,5,7,7, -pentamethyl-1, 2, 4-trioxepane, 0.02 part of styrene and 0.002 part of styrene; the material B comprises the following components in parts by mass: 100 parts of polypropylene, 20 parts of antioxidant 1024 (BASF China Co., Ltd.) and 0.03 part of dibutyltin dilaurate; wherein the mass ratio of the material A to the material B is 95: 5.
Example 3
The difference between the present embodiment and embodiment 1 is that the formulation of the A, B material is different, and the material a of the present embodiment includes the following components in parts by mass: 100 parts of polypropylene (melt index is 9.5g/10min), 1.5 parts of zinc dimethyldithiocarbamate, 3 parts of vinyltrimethoxysilane, 3,5,7,7, -pentamethyl-1, 2, 4-trioxepane and 0.002 part of styrene; the material B comprises the following components in parts by mass: 100 parts of polypropylene, 101020 parts of antioxidant and 0.03 part of stannous octoate; wherein the mass ratio of the material A to the material B is 95: 5.
Example 4
The difference between the present embodiment and embodiment 1 is that the formulation of the A, B material is different, and the material a of the present embodiment includes the following components in parts by mass: 100 parts of polypropylene (15.0 g/10 min; melting point: 15.0g/10 min; trivianite EPF 30R), 5 parts of zinc dimethyldithiocarbamate, 4 parts of 3- (methacryloyl) propyltrimethoxysilane, 0.01 part of 3,3,5,7,7, -pentamethyl-1, 2, 4-trioxepane and 0.001 part of styrene; the material B comprises the following components in parts by mass: 100 parts of polypropylene, 101010 parts of antioxidant and 0.01 part of dibutyltin dilaurate; wherein the mass ratio of the material A to the material B is 92: 8.
Example 5
The difference between the present embodiment and embodiment 1 is that the formulation of the A, B material is different, and the material a of the present embodiment includes the following components in parts by mass: 100 parts of polypropylene (Basel HP456J, melt: 3.4g/10min), 3 parts of zinc dimethyldithiocarbamate (Kandis chemical Co., Ltd.), 2.6 parts of 3- (methacryloyl) propyltrimethoxysilane, 3,5,7,7, -pentamethyl-1, 2, 4-trioxepane, 0.015 part of styrene and 0.0015 part of styrene; the material B comprises the following components in parts by mass: 100 parts of polypropylene, 10106 parts of antioxidant and 0.05 part of dibutyltin dilaurate; wherein the mass ratio of the material A to the material B is 96: 4.
Example 6
The difference between the present embodiment and embodiment 1 is that the formulation of the A, B material is different, and the material a of the present embodiment includes the following components in parts by mass: 100 portions of polypropylene (melt index: 3.4g/10min), 7.5 portions of zinc dimethyldithiocarbamate, 4.5 portions of 3- (methacryloyl) propyltrimethoxysilane, 0.15 portion of 3,3,5,7,7, -pentamethyl-1, 2, 4-trioxepane and 0.002 portion of styrene; the material B comprises the following components in parts by mass: 100 parts of polypropylene, 101025 parts of antioxidant and 0.05 part of dibutyltin dilaurate; wherein the mass ratio of the material A to the material B is 95: 5.
Example 7
The difference between the present embodiment and embodiment 1 is that the formulation of the A, B material is different, and the material a of the present embodiment includes the following components in parts by mass: 100 parts of polypropylene (melt: 9.5g/10min), 1 part of zinc dimethyldithiocarbamate, 1.5 parts of 3- (methacryloyl) propyltrimethoxysilane, 0.01 part of 3,3,5,7,7, -pentamethyl-1, 2, 4-trioxepane and 0.001 part of styrene; the material B comprises the following components in parts by mass: 100 parts of polypropylene, 10105 parts of antioxidant and 0.05 part of dibutyltin dilaurate; wherein the mass ratio of the material A to the material B is 95: 5.
Comparative example 1
The difference between the comparative example and the example 1 is that the formulation of the A, B material is different, and the A material of the comparative example comprises the following components in parts by mass: 100 portions of polypropylene (melt index: 3.6g/10min), 0.5 portion of zinc dimethyldithiocarbamate, 0.5 portion of 3- (methacryloyl) propyltrimethoxysilane, 0.01 portion of 3,3,5,7,7, -pentamethyl-1, 2, 4-trioxepane and 0.001 portion of styrene; the material B comprises the following components in parts by mass: 100 parts of polypropylene, 10105 parts of antioxidant and 0.05 part of dibutyltin dilaurate; wherein the mass ratio of the material A to the material B is 95: 5.
Comparative example 2
The difference between the comparative example and the example 1 is that 0.02 part of benzoyl peroxide is added to the material A as an initiator instead of trioxepanes.
Comparative example 3
The difference between the comparative example and the example 1 is that 3 parts of vinyltriethoxysilane is added as a silane grafting agent instead of the trimethoxysilane material in the A material.
Comparative example 4
The difference between the comparative example and the example 1 is that the A material is not added with styrene as an auxiliary crosslinking agent.
Comparative example 5
The difference between the comparative example and the example 1 is that the mass ratio of the material A to the material B is 88: 12.
Comparative example 6
The comparative example differs from example 1 in that the amount of zinc dimethyldithiocarbamate added to batch A is 0.1 part.
Comparative example 7
The comparative example differs from example 1 in that 3- (methacryloyl) propyltrimethoxysilane was added in an amount of 10 parts in feed A.
Comparative example 8
The difference between this comparative example and example 1 is that 3,3,5,7,7, -pentamethyl-1, 2, 4-trioxepane is added in an amount of 1 part in feed A.
Comparative example 9
The difference between this comparative example and example 1 is that the melt index of the polypropylene in batch A is 30g/10min (Yanshan petrochemical K7726).
Examples of effects
The crosslinked polypropylene materials prepared in examples 1 to 7 and comparative examples 1 to 9 were tested for mechanical properties, wherein the yield strength, the breaking strength, the elongation at break, the flexural strength, the izod impact strength, and the simple beam impact strength were tested according to the test method in GB/T18743, the heat distortion temperature was tested according to the method in GB/T1633 at 0.45MPa, and the gel fraction was tested according to the method in GB/T18474; the results of the tests on the crosslinked polypropylene material are shown in table 1;
table 1: performance testing of the crosslinked Polypropylene materials prepared in examples 1 to 7 and comparative examples 1 to 9
As can be seen from Table 1, the cross-linked polypropylene materials prepared in examples 1-7 have a gel fraction of 43% or more, a yield strength of 38.9MPa or more, and a heat distortion temperature of 128.2 ℃ or more, which indicates that the cross-linked polypropylene materials prepared according to the technical scheme provided by the present invention have a good gel fraction, and thus can be obtained with good mechanical properties and heat distortion temperature;
it can be seen from the data of example 1 and comparative example 1 that when too little degradation inhibitor and silane grafting agent are added, the degree of crosslinking of the crosslinking reaction is reduced, so that the mechanical properties and heat resistance of the product are not significantly improved; as can be seen from the data of example 1 and comparative example 2, when the trioxepane type initiator is changed into benzoyl peroxide, the gel fraction and the thermal deformation temperature of the prepared crosslinked polypropylene material are obviously reduced, which indicates that the selection of the initiator can influence the crosslinking degree of the reaction, thereby influencing the mechanical property and the heat resistance of the material; it can be seen from the data of example 1 and comparative example 3 that when the selected silane grafting agent is triethoxysilane, the effect of extrusion granulation is affected during the preparation process, and further the gel fraction of the product obtained by the crosslinking reaction is reduced by 46.30% compared with the gel fraction in example 1, and the reduction of the gel fraction causes corresponding reduction of the mechanical properties and heat resistance of the product; as can be seen from the data of example 1 and comparative example 4, when no styrenic co-crosslinking agent was added, the crosslinking reaction was insufficient, as evidenced by a decrease in the gel fraction of the material; as can be seen from the data of example 1 and comparative example 5, when the proportion of the material A and the material B is changed, the gel rate of the product is also influenced, and the mechanical property and the heat resistance of the product are further influenced; as can be seen from the data of example 1 and comparative example 6, when too little degradation inhibitor is added, the degradation of polypropylene cannot be effectively inhibited, and the degradation of polypropylene increases, on the one hand, the raw materials capable of reacting are reduced, on the other hand, the subsequent crosslinking reaction is also inhibited, so that the crosslinking degree of the prepared material is remarkably reduced, and compared with the material in example 1, the gel fraction is reduced by 51.85%; as can be seen from the data of example 1 and comparative example 7, when the content of the silane grafting agent is increased, there is little influence on the properties of the material, but the production efficiency is lowered and resources are also wasted; it can be seen from the data of example 1 and comparative example 8 that when the amount of the initiator is too large, the gel fraction of the material is significantly reduced, compared with example 1, the gel fraction is reduced by 74.07%, the heat distortion temperature is also significantly reduced, only 120.9 ℃ and 11.2 ℃ compared with the heat distortion temperature of the material in example 1, because excessive addition of the initiator causes degradation of the polypropylene, thereby inhibiting the crosslinking reaction; as can be seen from the data of example 1 and comparative example 9, when the melt index of the polypropylene is too high, although the degree of crosslinking is more than 40% after crosslinking, the heat distortion temperature is also significantly increased (K7726 heat distortion temperature 122.3 ℃), but the overall strength is lower; the reason is that the high melt index corresponds to a smaller molecular weight, and the fundamental properties of the PP as a substrate, such as tensile, yield, bending, impact resistance, etc., are lower than those of the PP as a low melt index.
Finally, it should be noted that the above embodiments are intended to illustrate the technical solutions of the present invention and not to limit the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The silane grafted polypropylene is characterized by comprising the following components in parts by mass: 100 parts of polypropylene, 1-8 parts of degradation inhibitor, 1.5-4.5 parts of silane grafting agent, 0.01-0.2 part of initiator and 0.001-0.01 part of auxiliary crosslinking agent.
2. The silane-grafted polypropylene according to claim 1, comprising the following components in parts by mass: 100 parts of polypropylene, 1.5-7.5 parts of degradation inhibitor, 2.5-4.5 parts of silane grafting agent, 0.01-0.02 part of initiator and 0.001-0.002 part of assistant crosslinking agent.
3. The silane-grafted polypropylene according to claim 1, wherein the melt index of the polypropylene is 3 to 20 g/min.
4. The silane-grafted polypropylene of claim 1, wherein the degradation inhibitor comprises a dithiocarbamate, a dithiocarbamate; the silane grafting agent comprises trimethoxy silane substances; the initiator comprises trioxepane substances; the auxiliary crosslinking agent comprises a styrene material.
5. The silane-grafted polypropylene of claim 1, wherein the degradation inhibitor comprises zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate or zinc dibutyldithiocarbamate; the silane grafting agent comprises 3- (methacryloyl) propyl trimethoxy silane, vinyl trimethoxy silane, 3-aminopropyl trimethoxy silane or methyl propyl acyloxy propyl trimethoxy silane.
6. The process for preparing silane-grafted polypropylene according to any one of claims 1 to 5, comprising in particular the steps of: the components of the silane grafted polypropylene are uniformly mixed, extruded, granulated and dried to obtain the silane grafted polypropylene.
7. A cross-linked polypropylene material is characterized by comprising a material A and a material B;
the material A is the silane grafted polypropylene of any one of claims 1 to 5;
the material B comprises the following components in parts by mass: 100 parts of polypropylene, 5-20 parts of antioxidant and 0.01-0.05 part of catalyst.
8. The cross-linked polypropylene material of claim 7, wherein the catalyst comprises an organotin species.
9. The cross-linked polypropylene material according to claim 7, wherein the mass ratio of the material A to the material B is (92-96): (4-8).
10. A method for preparing a cross-linked polypropylene material according to any one of claims 7 to 9, comprising the steps of: uniformly mixing the material A and the material B, and carrying out crosslinking reaction after extrusion or injection molding to obtain a crosslinked polypropylene material;
the crosslinking reaction is carried out by soaking in water at 70-100 ℃ or steaming for 16-32 h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115011058A (en) * | 2022-07-11 | 2022-09-06 | 青岛科技大学 | Reinforced polypropylene composite material and preparation method thereof |
| CN115785582A (en) * | 2022-12-21 | 2023-03-14 | 日丰新材有限公司 | Environment-friendly efficient silane crosslinked polypropylene material and preparation method thereof |
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