CN110564058A - Green intumescent flame-retardant polypropylene and preparation method thereof - Google Patents
Green intumescent flame-retardant polypropylene and preparation method thereof Download PDFInfo
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- CN110564058A CN110564058A CN201910864723.9A CN201910864723A CN110564058A CN 110564058 A CN110564058 A CN 110564058A CN 201910864723 A CN201910864723 A CN 201910864723A CN 110564058 A CN110564058 A CN 110564058A
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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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
- C08L2201/02—Flame or fire retardant/resistant
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to green intumescent flame retardant polypropylene and a preparation method thereof. The flame-retardant polypropylene comprises 75 parts by weight of polypropylene, 18-22 parts by weight of green Intumescent Flame Retardant (IFR) and 3-7 parts by weight of Expandable Graphite (EG); wherein the green intumescent flame retardant is obtained by compounding lignin and ammonium polyphosphate. The green intumescent flame retardant polypropylene prepared by the invention has excellent flame retardant effect and no melting and dripping phenomena during combustion; and the flame retardant system is green, environment-friendly and efficient, the charring agent can be completely regenerated, the price is low, and the industrialization is easy to realize.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to green intumescent flame retardant polypropylene and a preparation method thereof.
Background
The polypropylene (PP) is widely applied as a general plastic, has good processing performance and mechanical performance, can meet the use requirements of half of devices, and has low price; in addition, the density of PP is only 0.9g/cm3The plastic is the lightest general plastic and is widely used in the fields of automobiles, household appliances, packaging materials and the like. However, the limited oxygen index is only about 18%, the material belongs to flammable materials, and molten drops and casting ignition phenomena are easy to occur in the combustion process. Therefore, the flame retardant property of PP has become a great hot spot of research nowadays.
The Intumescent Flame Retardant (IFR) has been widely used in the field of flame retardant polypropylene due to its advantages of low toxicity, high efficiency, environmental protection, etc. Compared with inorganic flame retardants, the addition amount of IFR in PP is obviously reduced, but the addition amount is usually more than 30 wt% to meet the requirement of flame retardance, which often deteriorates the mechanical properties of high polymer materials. In addition, Pentaerythritol (PER) is commonly used as a char-forming agent in the conventional intumescent flame retardant, and the molecular weight of the char-forming agent is low, so that the char-forming agent is easy to precipitate and migrate to the surface of a flame-retardant high polymer material in the process of storage or use, thereby deteriorating the comprehensive performance of the material.
Lignin (Lig) is used as the second largest natural polymer material in nature, and the specific molecular structure of the ligin determines that the ligin is expected to be used as a char-forming agent and an intumescent flame retardant. Lig is mainly derived from byproducts of industrial paper making and bioethanol production, and has a low utilization rate in chemicals, not more than 5%. Therefore, the improvement of the application additional value of the lignin is just in line with the era concept of sustainable development. However, the lignin directly used as a char-forming agent for an intumescent flame retardant has poor char-forming ability, and is difficult to meet the expected flame retardant requirement, especially difficult to solve the molten drop phenomenon existing in the combustion process. However, when the lignin is partially used for replacing pentaerythritol, precipitation and migration phenomena still exist.
The graphite crystal of the Expandable Graphite (EG) is a hexagonal net plane layered structure consisting of carbon elements, has the advantages of no toxicity, no pollution and the like, and can achieve good flame retardant effect when used alone or mixed with other flame retardants. The action principle is as follows: at high temperature, the expandable graphite expands rapidly to suffocate flame, and the generated graphite expansion material covers the surface of the base material to isolate the contact of heat energy radiation and oxygen; acid radicals in the interlayer are released during expansion, so that the carbonization of the base material is promoted, and a good effect is achieved through various flame-retardant modes.
Disclosure of Invention
In order to solve the technical problems of the traditional intumescent flame retardant and simultaneously improve the application added value of lignin which is a byproduct in the paper industry, the invention provides green intumescent flame retardant polypropylene and a preparation method thereof. Renewable lignin with wide sources is used as a char forming agent to be compounded with ammonium polyphosphate to form an intumescent flame retardant, and expandable graphite is introduced to be used as a synergist on the basis, so that the green intumescent flame retardant polypropylene with good flame retardant property can be obtained.
In order to achieve the purpose, the invention provides a green intumescent flame retardant polypropylene, and the formula of the green intumescent flame retardant polypropylene is recorded as follows in parts by weight: 75 parts of polypropylene, 18-22 parts of green intumescent flame retardant and 3-7 parts of flame retardant synergist.
The green intumescent flame retardant used in the invention consists of lignin and ammonium polyphosphate, wherein the lignin is alkali lignin or enzymolysis lignin.
The mass ratio of the lignin to the ammonium polyphosphate used in the invention is 2:2-4, and the optimal ratio is 2: 3.
The flame-retardant synergist used in the invention is expandable graphite; the expansion ratio is 280-320 times, and the size range is 70-90 meshes.
In order to better achieve the aim of the invention, the invention also provides a preparation method of the green intumescent flame retardant polypropylene, which comprises the following steps: uniformly mixing lignin and ammonium polyphosphate by a ball mill according to a certain proportion, uniformly mixing the mixed IFR and expandable graphite, heating and melting PP for 4-5min at 170-190 ℃ by an internal mixer, adding a flame retardant, and further blending for 3-4min to obtain the green intumescent flame retardant polypropylene.
The invention has the beneficial effects that:
The lignin and the expandable graphite adopted by the invention have rich sources, are nontoxic and pollution-free, and are green and environment-friendly. The lignin completely replaces pentaerythritol, so that the material cost can be effectively reduced on the premise of meeting the flame retardant property, the expandable graphite expands rapidly when being heated at high temperature, and the generated graphite expanded material covers the surface of the base material, so that the heat radiation and the oxygen contact can be isolated; in addition, acid radical ions released from the interior of the interlayer in the thermal decomposition process can promote the carbonization of the base material, so that a good effect is achieved through various flame-retardant modes.
Drawings
FIG. 1 is a comparison graph of contact angles before and after placing for 7 days of the conventional type flame retardant PP (a) and the green intumescent flame retardant PP (b), wherein (a1) and (b1) are contact angle graphs before placing, and (a2) and (b2) are contact angle graphs after placing for 7 days.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to limit the scope of the present invention. The polypropylene used in the examples below was weathered T30S; ammonium polyphosphate (APP), degree of polymerization n >1000, Hangzhou Jieisi flame retardant chemical Co., Ltd; alkali lignin (Lig), jinan yanghai materials ltd; enzymolysis of lignin, Dalian research institute of petrochemical industry; expandable Graphite (EG), size range 70-90 mesh, lingshou county gold industry processing plant. During the preparation process of the green intumescent flame retardant polypropylene, lignin is used for replacing alkali lignin and enzymatic hydrolysis lignin.
Examples 1 to 12
According to the formula shown in the table 1, lignin and ammonium polyphosphate are uniformly mixed by a ball mill according to a certain proportion, then the mixed IFR and expandable graphite are uniformly mixed, PP is heated and melted for 4-5min at the temperature of 170-190 ℃ by an internal mixer, and then a flame retardant is added for further blending for 3-4min to obtain the green intumescent flame retardant polypropylene. The flame retardant property test results of the obtained green intumescent flame retardant polypropylene are shown in table 1.
Comparative example 1
Only PP and EG are adopted to prepare the flame-retardant polypropylene material.
The components are uniformly mixed according to the formula shown in the table 1, and then are melted and blended by an internal mixer to obtain the green intumescent flame retardant polypropylene. The results of the performance tests of the flame retardant material obtained are shown in table 1.
Comparative example 2
The weight portion ratio of the ammonium polyphosphate to the lignin is 2:1, and the flame-retardant polypropylene material is prepared.
The components are uniformly mixed according to the formula shown in the table 1, and then are melted and blended by an internal mixer to obtain the green intumescent flame retardant polypropylene. The results of the performance tests of the flame retardant material obtained are shown in table 1.
Comparative example 3
The weight portion ratio of the ammonium polyphosphate to the lignin is 3:2, and the flame-retardant polypropylene material is prepared.
The components are uniformly mixed according to the formula shown in the table 1, and then are melted and blended by an internal mixer to obtain the green intumescent flame retardant polypropylene. The results of the performance tests of the flame retardant material obtained are shown in table 1.
Comparative example 4
The weight portion ratio of the ammonium polyphosphate to the lignin is 1:1, and the flame-retardant polypropylene material is prepared.
The components are uniformly mixed according to the formula shown in the table 1, and then are melted and blended by an internal mixer to obtain the green intumescent flame retardant polypropylene. The results of the performance tests of the flame retardant material obtained are shown in table 1.
Comparative example 5
The weight ratio of the ammonium polyphosphate to the enzymolysis lignin is 3:2, and the flame-retardant polypropylene material is prepared.
The components are uniformly mixed according to the formula shown in the table 1, and then are melted and blended by an internal mixer to obtain the green intumescent flame retardant polypropylene. The results of the performance tests of the flame retardant material obtained are shown in table 1.
Comparative example 6
The weight portion ratio of the ammonium polyphosphate to the pentaerythritol is 3:2, and the flame-retardant polypropylene material is prepared. The components are uniformly mixed according to the formula shown in the table 1, and then are melted and blended by an internal mixer to obtain the traditional flame-retardant polypropylene. The results of the performance tests of the flame retardant material obtained are shown in table 1.
TABLE 1
Remarking: N.R- -no grade.
as can be seen from Table 1, when the ratio of APP to lignin is 3:2, the flame-retardant PP shows a higher limiting oxygen index, and the addition of EG, namely examples 1-12, can improve the limiting oxygen index of the green intumescent flame-retardant polypropylene, which indicates that EG can effectively improve the flame-retardant performance of the system. In addition, with the increase of the amount of EG, the Limiting Oxygen Index (LOI) of the green intumescent flame retardant polypropylene shows a tendency of increasing and then decreasing, the flame retardant performance of the obtained green intumescent flame retardant polypropylene is respectively obviously higher than that of comparative examples 2-5, and particularly when the addition amount of EG is 5% (examples 5 and 11), the corresponding green intumescent flame retardant polypropylene can pass V-0 grade regardless of alkali lignin or enzymatic hydrolysis lignin.
In order to further show that the green intumescent flame retardant polypropylene prepared by taking lignin as a macromolecular char forming agent has the advantage of difficult precipitation, the prepared traditional flame retardant PP (pentaerythritol is taken as the char forming agent) and the sample strips of the green intumescent flame retardant PP are placed in the air at room temperature for 7 days, and fig. 1 is a contact angle comparison graph of the traditional flame retardant PP and the green intumescent flame retardant PP before and after the sample strips are placed for 7 days. The contact angles of the traditional flame-retardant PP and the green intumescent flame-retardant PP are respectively 83.1 degrees and 84.1 degrees, after the PP is placed for 7 days, the contact angle of the traditional flame-retardant PP is reduced to 68.7 degrees, which is probably caused by the fact that PER is easy to migrate to the surface of the PP, while the contact angle of the green intumescent flame-retardant PP is reduced to 81.7 degrees, which shows that the lignin serving as a macromolecular char forming agent for preparing the green intumescent flame-retardant polypropylene has certain advantages of being difficult to separate out.
Claims (6)
1. The green intumescent flame-retardant polypropylene is characterized by comprising the following components in parts by weight: 75 parts of polypropylene, 18-22 parts of green intumescent flame retardant and 3-7 parts of flame retardant synergist expandable graphite.
2. The green intumescent flame retardant polypropylene of claim 1, wherein the green intumescent flame retardant is composed of lignin and ammonium polyphosphate, wherein the lignin is alkali lignin or enzymatic hydrolysis lignin.
3. The green intumescent flame retardant polypropylene of claim 2, wherein the mass ratio of the lignin to the ammonium polyphosphate is 2: 2-4.
4. The green intumescent flame retardant polypropylene of claim 2, wherein the mass ratio of lignin to ammonium polyphosphate is 2: 3.
5. The green intumescent flame retardant polypropylene of claim 1, wherein the expandable graphite has an expansion ratio of 280 to 320 times and a size range of 70 to 90 mesh.
6. The preparation method of the green intumescent flame retardant polypropylene as claimed in claim 1, characterized in that the preparation method comprises the following steps: uniformly mixing lignin and ammonium polyphosphate by a ball mill according to a certain proportion, uniformly mixing the mixed IFR and expandable graphite, heating and melting PP for 4-5min at 170-190 ℃ by an internal mixer, adding a flame retardant, and further blending for 3-4min to obtain the green intumescent flame retardant polypropylene.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113185777A (en) * | 2021-06-10 | 2021-07-30 | 中国科学院长春应用化学研究所 | High-flame-retardant polypropylene foamed bead as well as preparation method and application thereof |
| CN115181352A (en) * | 2022-08-15 | 2022-10-14 | 华北电力大学（保定） | Flame-retardant material for cable sheath and preparation method thereof |
| CN116731414A (en) * | 2023-04-13 | 2023-09-12 | 上海滩泰科技有限公司 | Flame-retardant polymer material |
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| CN109370047A (en) * | 2018-10-10 | 2019-02-22 | 常州大学 | A kind of environment-friendly type flame-proof polypropylene and preparation method thereof |
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| CN109370047A (en) * | 2018-10-10 | 2019-02-22 | 常州大学 | A kind of environment-friendly type flame-proof polypropylene and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113185777A (en) * | 2021-06-10 | 2021-07-30 | 中国科学院长春应用化学研究所 | High-flame-retardant polypropylene foamed bead as well as preparation method and application thereof |
| CN115181352A (en) * | 2022-08-15 | 2022-10-14 | 华北电力大学（保定） | Flame-retardant material for cable sheath and preparation method thereof |
| CN115181352B (en) * | 2022-08-15 | 2023-12-22 | 华北电力大学（保定） | Flame-retardant material for cable sheath and preparation method thereof |
| CN116731414A (en) * | 2023-04-13 | 2023-09-12 | 上海滩泰科技有限公司 | Flame-retardant polymer material |
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