CN112724524A - Biodegradable flame-retardant polypropylene composite material and preparation method thereof - Google Patents
Biodegradable flame-retardant polypropylene composite material and preparation method thereof Download PDFInfo
- Publication number
- CN112724524A CN112724524A CN202011582958.8A CN202011582958A CN112724524A CN 112724524 A CN112724524 A CN 112724524A CN 202011582958 A CN202011582958 A CN 202011582958A CN 112724524 A CN112724524 A CN 112724524A
- Authority
- CN
- China
- Prior art keywords
- starch
- hypophosphite
- composite material
- polypropylene composite
- antioxidant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/02—Esters
- C08B31/06—Esters of inorganic acids
- C08B31/066—Starch phosphates, e.g. phosphorylated starch
-
- 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
- C08L23/14—Copolymers of propene
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
Landscapes
- Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a biodegradable flame-retardant polypropylene composite material which is prepared from 80-85 parts of polypropylene resin, 15-20 parts of hypophosphite starch, 0.3-0.5 part of antioxidant and 0.3-0.5 part of lubricant in parts by weight. The hypophosphite starch added in the invention can greatly improve the lipophilicity of the esterified starch, thereby improving the compatibility of the esterified starch with polymer materials, having good dispersibility in polypropylene and improving the strength of the materials.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a biodegradable flame-retardant polypropylene composite material and a preparation method thereof.
Background
Polypropylene (PP) has been widely used in various industries due to its advantages of good stability, excellent mechanical properties, low price, etc., but the material degrades very slowly in natural environment, so that the "white pollution" brought by the waste products causes little harm to the environment, which hinders the further development of PP. At present, two methods of incineration and landfill are mainly adopted when PP waste is treated, although the two treatment methods reduce white pollution to a certain extent, the problems of air pollution, soil pollution, water pollution and the like are brought along with the white pollution, and the symptom that the PP waste pollutes the environment cannot be eradicated.
Biodegradable plastics refer to a class of plastics that are degraded by the action of microorganisms such as bacteria, molds (fungi), and algae that exist in nature. The ideal biodegradable plastic is a high polymer material which has excellent service performance, can be completely decomposed by microorganisms in the environment after being discarded, and is finally degraded into carbon dioxide and water. Most pure polymers are not easily decomposed by microorganisms, and although the PP material can be biodegraded in the environment, the degradation time is very long, and the biodegradation performance of the PP can be improved by adding starch.
In the prior art, starch is used alone, so that the defects of non-flame-retardant material and poor compatibility with a base material exist, the mechanical property of the polypropylene composite material is greatly influenced, and the polypropylene composite material is low in strength and poor in thermal stability.
Disclosure of Invention
The invention aims to provide a biodegradable flame-retardant polypropylene composite material and a preparation method thereof, which are used for solving the problems in the background art, and can ensure the biodegradability of the material and increase the flame-retardant property of the material.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a biodegradable flame-retardant polypropylene composite material, which is prepared from 80-85 parts of polypropylene resin, 15-20 parts of hypophosphite starch, 0.3-0.5 part of antioxidant and 0.3-0.5 part of lubricant in parts by weight.
As a further scheme of the invention: the polypropylene resin is at least one of copolymerized polypropylene and homopolymerized polypropylene.
As a further scheme of the invention: the antioxidant is at least one of alkyl monophenol antioxidant, azacyclo-polyphenol antioxidant, phosphite antioxidant and thiobisphenol antioxidant.
As a further scheme of the invention: the lubricant is at least one selected from a metal soap lubricant and a silicone lubricant.
As a further scheme of the invention: the preparation method of the hypophosphite starch comprises the following steps:
mixing materials: sufficiently dissolving hypophosphite and urea in distilled water, adjusting the pH value to 5-6 and the temperature to 20-25 ℃, adding starch, and sufficiently stirring for 30min to obtain a mixed material;
pre-drying: filtering the mixed material, and pre-drying at 40-50 ℃ until the water content is not lower than 5% to obtain a pre-dried material;
esterification: reacting the pre-dried material at the temperature of 155-165 ℃ for 2-2.5h to obtain hypophosphite starch;
wherein the mass ratio of the hypophosphite to the urea to the distilled water to the starch is (5-8): (9-10): 100:100.
As a further scheme of the invention: the hypophosphite is at least one of sodium hypophosphite and magnesium hypophosphite.
As a further scheme of the invention: the starch is at least one of corn starch, sweet potato starch and mung bean starch.
The second aspect of the invention discloses a preparation method of the biodegradable flame-retardant polypropylene composite material, which comprises the following steps:
s1: weighing the polypropylene resin, the antioxidant and the lubricant according to the proportion, adding the mixture into a high-speed stirrer, and mixing for 3-5min to obtain a mixed material;
s2: and (4) adding the mixed material prepared in the step (S1) into a double-screw extruder through a main feeding hopper, adding the starch hypophosphite through a side feeding hopper, and melting, extruding and drying to obtain the biodegradable flame-retardant polypropylene composite material.
Furthermore, the temperature of the double-screw extruder material cylinder is 190-.
Compared with the prior art, the invention has the beneficial effects that:
the hypophosphite starch added in the invention can greatly improve the lipophilicity of the esterified starch, thereby improving the compatibility of the esterified starch with polymer materials, having good dispersibility in polypropylene and improving the strength of the materials.
Hypophosphite has higher phosphorus content, so the hypophosphite has the basic flame-retardant characteristic of a phosphorus flame retardant, has condensed phase flame retardance while being flame-retardant in a gas phase, is decomposed by heating at high temperature, and can capture more active O and OH free radicals in the air by (PO) free radicals formed by P-O, reduce the oxygen content in a limited space to a certain extent, terminate the combustion chain reaction, decompose hypophosphorous acid into metaphosphoric acid by absorbing heat in the heating process, further decompose the metaphosphoric acid, can effectively absorb OH and NH 2-generated in a matrix, and absorb heat in a certain range; on the other hand, the hypophosphite can promote the starch to be carbonized, and a compact carbon layer is formed to cover the surface of a combustion object, so that air is isolated to achieve the flame retardant effect. The synergistic effect and high flame-retarding efficiency.
The biodegradation rate of the polypropylene material can be improved by adding the hypophosphite starch, the starch is degraded in the starch polymer material at a high speed, and after the starch is degraded, the polypropylene material generates micropores, so that the surface area of the material is increased, the end group of the polymer material is exposed, and the further degradation of the material is promoted.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the 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 invention esterifies starch by hypophosphite, improves the lipophilicity of the starch, has good dispersibility in polypropylene, improves the strength of the material, improves the synergistic flame-retardant effect of the hypophosphite and the starch, can take away more heat when the material is heated and decomposed, and simultaneously forms a compact carbon layer on the surface of a polymer through catalytic action to isolate oxygen, thereby greatly improving the flame-retardant property of the composite material.
The starch esterified by hypophosphite can greatly improve the lipophilicity of the starch, thereby improving the compatibility of the starch with polymer materials. The powder is well combined with the polypropylene matrix, and the impact and tensile properties are less influenced; the invention utilizes the synergistic flame-retardant effect of phosphate radical and starch, and the hypophosphite radical can absorb heat during decomposition and simultaneously can more effectively promote the carbon forming process of the composite material, so that the formed carbon layer is more compact and uniform, the radiation of external heat and the entering of oxygen are blocked, and the heat release rate is obviously reduced, thereby greatly improving the flame-retardant property of the composite material; the biodegradation rate of the polypropylene material can be improved by adding the hypophosphite starch, the degradation speed of the starch in the starch polymer material is higher, and after the starch is degraded, micropores are generated in the material, so that the surface area of the material is increased, the end group of the polymer material is exposed, and the further degradation of the material is promoted.
The following examples and comparative examples employ the following raw material specific information:
copolymer polypropylene resin, designation K7227H, manufacturer: martial arts and Chinese petrifaction
Homo-polypropylene resin, designation SZ30S, manufacturer: martial arts and Chinese petrifaction
Sodium hypophosphite, manufacturer: changchang chemical Co Ltd, Zhang Home Port City
Urea, manufacturer: shandong Deg chemical engineering Co Ltd
Lubricant: EBS, designation 130P, manufacturer: indonesia PT CMS; CaSt, designation CV500, manufacturer: dongguan Hanwei tea
Antioxidant 1076, manufacturer: tianjin Lianlong New Material Ltd
Antioxidant 168, manufacturer: tianjin Lianlong New Material Ltd
Antioxidant 1010, manufacturer: tianjin Lianlong New Material Ltd
All other components are common commercial raw materials unless otherwise specified.
It is understood that the above raw material reagents are only examples of some specific embodiments of the present invention, so as to make the technical scheme of the present invention more clear, and do not represent that the present invention can only adopt the above reagents, particularly, the scope of the claims is subject to. In addition, "parts" described in examples and comparative examples mean parts by weight unless otherwise specified.
Example 1
The biodegradable flame-retardant polypropylene composite material is prepared from the following raw materials in parts by weight:
the preparation method comprises the following steps:
s1, dissolving 5g of sodium hypophosphite and 10g of urea in 100ml of distilled water, adjusting the pH value to 5, adding 100g of corn starch, stirring for 30min at 23 ℃, filtering, predrying at 45 ℃ until the water content is 5%, heating to 160 ℃, and carrying out esterification reaction for 2h to obtain the hypophosphite corn starch.
S2, weighing the polypropylene resin, the antioxidant and the lubricant according to the proportion, adding the mixture into a high-speed stirrer, and mixing for 5min to obtain a mixed material;
s3, adding the mixed material prepared in the step S2 into a double-screw extruder through a main feeding hopper, adding the hypophosphite corn starch prepared in the step S1 through a side feeding hopper, and melting, extruding and drying to prepare the biodegradable flame-retardant polypropylene composite material; wherein the temperature of a charging barrel of the double-screw extruder is 220 ℃, the rotating speed of a screw is 500r/min, the rotating speed of a main machine is 22Hz, and the vacuum degree is-0.08 MPa.
Example 2
The biodegradable flame-retardant polypropylene composite material is prepared from the following raw materials in parts by weight:
the preparation method comprises the following steps:
s1, dissolving 5g of sodium hypophosphite and 10g of urea in 100ml of distilled water, adjusting the pH value to 5, adding 100g of sweet potato starch, stirring for 30min at 23 ℃, filtering, predrying at 45 ℃ until the water content is 5%, heating to 160 ℃, and carrying out esterification reaction for 2h to obtain the hypophosphite sweet potato starch.
S2, weighing the polypropylene resin, the antioxidant and the lubricant according to the proportion, adding the mixture into a high-speed stirrer, and mixing for 5min to obtain a mixed material;
s3, adding the mixed material prepared in the step S2 into a double-screw extruder through a main feeding hopper, adding the hypophosphite sweet potato starch prepared in the step S1 through a side feeding hopper, and melting, extruding and drying to prepare the biodegradable flame-retardant polypropylene composite material; wherein the temperature of a charging barrel of the double-screw extruder is 220 ℃, the rotating speed of a screw is 500r/min, the rotating speed of a main machine is 22Hz, and the vacuum degree is-0.08 MPa.
Example 3
The biodegradable flame-retardant polypropylene composite material is prepared from the following raw materials in parts by weight:
the preparation method comprises the following steps:
s1, dissolving 5g of sodium hypophosphite and 10g of urea in 100ml of distilled water, adjusting the pH value to 5, adding 100g of mung bean starch, stirring for 30min at 23 ℃, filtering, predrying at 45 ℃ until the water content is 5%, heating to 160 ℃, and carrying out esterification reaction for 2h to obtain the hypophosphite mung bean starch.
S2, weighing the polypropylene resin, the antioxidant and the lubricant according to the proportion, adding the mixture into a high-speed stirrer, and mixing for 5min to obtain a mixed material;
s3, adding the mixed material prepared in the step S2 into a double-screw extruder through a main feeding hopper, adding the hypophosphite mung bean starch prepared in the step S1 through a side feeding hopper, and melting, extruding and drying to prepare the biodegradable flame-retardant polypropylene composite material; wherein the temperature of a charging barrel of the double-screw extruder is 220 ℃, the rotating speed of a screw is 500r/min, the rotating speed of a main machine is 22Hz, and the vacuum degree is-0.08 MPa.
Comparative example 1
The difference from the example 1 is that the hypophosphite corn starch is replaced by the same weight part of corn starch, and the rest components and the preparation method are the same as the example 1.
Comparative example 2
The difference from the example 1 is that 20 parts of hypophosphite corn starch is replaced by 20 parts of phosphate corn starch, and the rest component proportion is completely the same as the example 1.
The preparation method comprises the following steps:
s1, dissolving 5g of sodium phosphate and 10g of urea in 100ml of distilled water, adjusting the pH value to 5, adding 100g of corn starch, stirring for 30min at 23 ℃, filtering, predrying at 45 ℃ until the water content is 5%, heating to 160 ℃, and carrying out esterification reaction for 2h to obtain the phosphate corn starch.
S2, weighing the polypropylene resin, the antioxidant and the lubricant according to the proportion, adding the mixture into a high-speed stirrer, and mixing for 5min to obtain a mixed material;
s3, adding the mixed material prepared in the step S2 into a double-screw extruder through a main feeding hopper, adding the phosphate corn starch prepared in the step S1 through a side feeding hopper, and melting, extruding and drying to prepare the biodegradable flame-retardant polypropylene composite material; wherein the temperature of a charging barrel of the double-screw extruder is 220 ℃, the rotating speed of a screw is 500r/min, the rotating speed of a main machine is 22Hz, and the vacuum degree is-0.08 MPa. The main physical property indexes of the polypropylene composite materials prepared in the above examples 1 to 3 and comparative examples 1 to 2 were measured according to the relevant test standards, and the test standards and test results of tensile strength, flexural modulus, impact strength, heat release rate are shown in table 1:
table 1: detection standards and detection results of the polypropylene composite materials in examples 1-3 and comparative examples 1-2
Note: the Heat Release Rate (HRR) refers to the amount of heat released per unit time by combustion of a material under specified test conditions. The larger the HRR, the lower the flame retardancy of the material; HRR is detected by a cone calorimeter according to the national standard GB/T16172-2007/ISO 5660-1: 2002, determination of the rate of heat release from combustion of the sample under specific conditions of thermal radiation for the composite. The degradation rate is detected by soil burying method, degrading the composite material by using microorganism group in soil, taking out the sample after 60 days, and measuring the weight loss change.
As can be seen from Table 1, the heat release rate in examples 1-3 is significantly lower than that in comparative examples 1-2, indicating that the polypropylene composite material prepared by adding the starch hypophosphite has good flame retardancy; from example 1 and comparative example 1, it can be seen that the degradation rate of the polypropylene composite material added with the hypophosphite corn starch is remarkably improved.
Although the present description is described in terms of embodiments, not every embodiment includes only a single embodiment, and such description is for clarity only, and those skilled in the art should be able to integrate the description as a whole, and the embodiments can be appropriately combined to form other embodiments as will be understood by those skilled in the art.
Therefore, the above description is only a preferred embodiment of the present application, and is not intended to limit the scope of the present application; all changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.
Claims (9)
1. The biodegradable flame-retardant polypropylene composite material is characterized by being prepared from 80-85 parts of polypropylene resin, 15-20 parts of hypophosphite starch, 0.3-0.5 part of antioxidant and 0.3-0.5 part of lubricant in parts by weight.
2. The biodegradable flame retardant polypropylene composite material according to claim 1, wherein the polypropylene resin is at least one of a co-polypropylene and a homo-polypropylene.
3. The biodegradable flame retardant polypropylene composite material as claimed in claim 1, wherein the antioxidant is at least one of alkyl monophenol antioxidant, azacyclo-phenol antioxidant, phosphite antioxidant, and thiobisphenol antioxidant.
4. The biodegradable flame retardant polypropylene composite material according to claim 1, wherein the lubricant is at least one selected from a metal soap lubricant and a silicone lubricant.
5. The biodegradable flame-retardant polypropylene composite material as claimed in claim 1, wherein the preparation method of the hypophosphite starch comprises the following steps:
mixing materials: sufficiently dissolving hypophosphite and urea in distilled water, adjusting the pH value to 5-6 and the temperature to 20-25 ℃, adding starch, and sufficiently stirring for 30min to obtain a mixed material;
pre-drying: filtering the mixed material, and predrying at 40-50 ℃ until the water content is not less than 5% to obtain a predried material;
esterification: reacting the pre-dried material at the temperature of 155-165 ℃ for 2-2.5h to obtain hypophosphite starch;
wherein the mass ratio of the hypophosphite to the urea to the distilled water to the starch is (5-8): (9-10): 100: 100.
6. the biodegradable flame retardant polypropylene composite material according to claim 5, wherein the hypophosphite is at least one of sodium hypophosphite and magnesium hypophosphite.
7. The biodegradable flame retardant polypropylene composite material as set forth in claim 5, wherein the starch is at least one of corn starch, sweet potato starch, mung bean starch.
8. The preparation method of the biodegradable flame retardant polypropylene composite material according to any one of claims 1 to 7, comprising the steps of:
weighing the polypropylene resin, the antioxidant and the lubricant according to the proportion, adding the mixture into a high-speed stirrer, and mixing for 3-5min to obtain a mixed material;
and adding the mixed material into a double-screw extruder through a main feeding hopper, adding hypophosphite starch through a side feeding hopper, and melting, extruding and drying to obtain the biodegradable flame-retardant polypropylene composite material.
9. The method for preparing the biodegradable flame-retardant polypropylene composite material as claimed in claim 8, wherein the temperature of the cylinder of the twin-screw extruder is 190-220 ℃, the rotation speed of the screw is 400-500r/min, the rotation speed of the host is 18-22Hz, and the vacuum degree is-0.06-0.08 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011582958.8A CN112724524B (en) | 2020-12-28 | 2020-12-28 | Biodegradable flame-retardant polypropylene composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011582958.8A CN112724524B (en) | 2020-12-28 | 2020-12-28 | Biodegradable flame-retardant polypropylene composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112724524A true CN112724524A (en) | 2021-04-30 |
| CN112724524B CN112724524B (en) | 2022-04-01 |
Family
ID=75607002
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011582958.8A Active CN112724524B (en) | 2020-12-28 | 2020-12-28 | Biodegradable flame-retardant polypropylene composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112724524B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6962950B1 (en) * | 1998-09-22 | 2005-11-08 | Novamont S.P.A. | Polymers of a hydrophobic nature, filled with starch complexes |
| US20070270527A1 (en) * | 2003-12-02 | 2007-11-22 | Takeshi Horie | Resin Composition, Molded Product From Resin Composition and Method for Preparing Resin Composition |
| CN103232677A (en) * | 2013-03-31 | 2013-08-07 | 青岛永卓真塑料制品有限公司 | ABS composite material with high toughness and high heat resistance |
| CN106496975A (en) * | 2016-09-29 | 2017-03-15 | 中国科学院宁波材料技术与工程研究所 | A kind of polylactic acid/starch intumescent flame-retardant composite and preparation method thereof |
| US20170137614A1 (en) * | 2014-03-28 | 2017-05-18 | Ursa Insulation, S.A. | Improved curable formaldehyde-free resin dispersion with reduced viscosity and mineral wool products produced therewith |
| CN108691239A (en) * | 2018-06-15 | 2018-10-23 | 西北民族大学 | A kind of preparation method and applications of composite modified cornstarch fire proofing |
| US20190382628A1 (en) * | 2018-06-19 | 2019-12-19 | Johns Manville | Starch and carboxylic acid binder compositions and articles made therewith |
| CN110964124A (en) * | 2019-12-20 | 2020-04-07 | 江南大学 | Modified starch for preparing halogen-free flame-retardant TPV composite material and preparation thereof |
| CN111234040A (en) * | 2020-01-09 | 2020-06-05 | 厦门大学 | Preparation method and application of urea modified starch |
| CN112063019A (en) * | 2020-08-06 | 2020-12-11 | 湖北工程学院 | Biomass composite ammonium polyphosphate intumescent flame retardant and preparation method and application thereof |
-
2020
- 2020-12-28 CN CN202011582958.8A patent/CN112724524B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6962950B1 (en) * | 1998-09-22 | 2005-11-08 | Novamont S.P.A. | Polymers of a hydrophobic nature, filled with starch complexes |
| US20070270527A1 (en) * | 2003-12-02 | 2007-11-22 | Takeshi Horie | Resin Composition, Molded Product From Resin Composition and Method for Preparing Resin Composition |
| CN103232677A (en) * | 2013-03-31 | 2013-08-07 | 青岛永卓真塑料制品有限公司 | ABS composite material with high toughness and high heat resistance |
| US20170137614A1 (en) * | 2014-03-28 | 2017-05-18 | Ursa Insulation, S.A. | Improved curable formaldehyde-free resin dispersion with reduced viscosity and mineral wool products produced therewith |
| CN106496975A (en) * | 2016-09-29 | 2017-03-15 | 中国科学院宁波材料技术与工程研究所 | A kind of polylactic acid/starch intumescent flame-retardant composite and preparation method thereof |
| CN108691239A (en) * | 2018-06-15 | 2018-10-23 | 西北民族大学 | A kind of preparation method and applications of composite modified cornstarch fire proofing |
| US20190382628A1 (en) * | 2018-06-19 | 2019-12-19 | Johns Manville | Starch and carboxylic acid binder compositions and articles made therewith |
| CN110964124A (en) * | 2019-12-20 | 2020-04-07 | 江南大学 | Modified starch for preparing halogen-free flame-retardant TPV composite material and preparation thereof |
| CN111234040A (en) * | 2020-01-09 | 2020-06-05 | 厦门大学 | Preparation method and application of urea modified starch |
| CN112063019A (en) * | 2020-08-06 | 2020-12-11 | 湖北工程学院 | Biomass composite ammonium polyphosphate intumescent flame retardant and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112724524B (en) | 2022-04-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2468051C2 (en) | Fire retardant resin composition | |
| EP1389630A1 (en) | Biodegradable polymer composition, filler therefor and molded article thereof | |
| CN103012904B (en) | Halogen-free flame-retardant master batch | |
| CN105133085A (en) | Preparation method of environmentally-friendly flame-retardant polyester bulked continuous filament | |
| CN115304913B (en) | Reinforced flame-retardant hypophosphite/nylon composite material with high glow wire ignition temperature and preparation method thereof | |
| CN115011078B (en) | Flame-retardant environment-friendly PET plastic and preparation method thereof | |
| CN114605746A (en) | Master batch for flame retardant material and preparation method thereof | |
| Yu et al. | Biomass intumescent flame retardant polyacrylonitrile composite: flame retardancy, smoke suppression and recycling | |
| Lu et al. | Flammability properties of intumescent vinyl acetate–ethylene copolymer emulsion including natural carbonization agent | |
| CN112724524B (en) | Biodegradable flame-retardant polypropylene composite material and preparation method thereof | |
| JP2023549040A (en) | Highly flame retardant halogen-free flame retardant composition system having high temperature and high shear resistance and its use | |
| CN111484520A (en) | Ethylene diamine tetramethylene aluminum phosphonate flame retardant and preparation method and application thereof | |
| CN113185817A (en) | Polylactic acid plastic containing composite flame retardant and preparation method thereof | |
| CN115975370B (en) | Halogen-free flame retardant TPU and preparation method thereof | |
| CN115197475B (en) | DOPO/ATMP modified chitosan-loaded aluminum-based single-component intumescent flame retardant as well as preparation method and application thereof | |
| CN110157096B (en) | Environment-friendly antistatic flame-retardant polypropylene material and preparation method thereof | |
| CN115322441B (en) | Method for producing aluminum hypophosphite flame retardant by utilizing sodium hypophosphite mother liquor | |
| CN1260323C (en) | Flame retardant composite from phosphorus, nitrogen systems | |
| CN113563486B (en) | Flame-retardant nanocellulose containing phosphorus nitrile group, preparation method and flame-retardant polylactic acid thereof | |
| CN113105725A (en) | Biodegradable material and preparation method and application thereof | |
| CN111423662A (en) | Flame-retardant PP plastic particle and preparation method thereof | |
| CN110981977A (en) | Flame-retardant cellulose and preparation method and application thereof | |
| CN114874456B (en) | Method for modifying natural lignin of halogen-free flame-retardant degradable plastic | |
| CN113416413B (en) | Glass fiber reinforced nylon 10T flame-retardant composite material and preparation method and application thereof | |
| CN114957931B (en) | High-anti-dripping flame-retardant thermoplastic polyester elastomer composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |