CN116218180B - Flame-retardant material - Google Patents
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- CN116218180B CN116218180B CN202310511116.0A CN202310511116A CN116218180B CN 116218180 B CN116218180 B CN 116218180B CN 202310511116 A CN202310511116 A CN 202310511116A CN 116218180 B CN116218180 B CN 116218180B
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention relates to the technical field of flame-retardant high polymer materials, in particular to a flame-retardant material and a preparation method thereof, wherein the flame-retardant material comprises polyhydroxyalkanoate, a halogen-free flame retardant and an auxiliary agent, and the halogen-free flame retardant comprises a bio-based phosphorus flame retardant, a bio-based polyhydroxyalkanoate and a bio-based nitrogen flame retardant. The flame-retardant material prepared by the method has the advantages of good comprehensive properties, no halogen, environmental protection, low addition amount of the flame retardant, and most of the flame-retardant material is a bio-based material, the flame-retardant effect reaches V-0 level, and the flame-retardant material can meet the flame-retardant requirements of the application fields of building materials, home textiles, aerospace, military industry, automobiles, packaging and the like, which need the flame-retardant properties of the material.
Description
Technical Field
The invention relates to the technical field of flame-retardant high polymer materials, in particular to a flame-retardant degradable polyhydroxyalkanoate PHA material.
Background
With the rapid development of economy, the living standard of people is increasingly improved, and the requirements of people on environmental quality are increasingly high. However, the application of the disposable plastic which is not degradable worldwide aggravates the white pollution of the human living environment. Common biodegradable materials at home and abroad such as polylactic acid (PLA), polycaprolactone (PCL), poly (adipic acid)/polybutylene terephthalate (PBAT), poly (butylene succinate) (PBS), polyhydroxyalkanoate (PHA) and the like develop well, the performance is continuously improved, and the application is more and more extensive, such as daily necessities, medical fields, packaging fields, catering fields and the like. However, the limited oxygen index of the biodegradable material is low, only about 20, and the biodegradable material is flammable under normal conditions, so that the biodegradable material is extremely limited in application fields requiring flame retardance.
Flame retardant biodegradable materials are mainly focused on PLA, PBS, PBAT, etc., as disclosed in the patent publication No. CN1733828A for realizing flame retardant type of polyester materials by synthetic means. The publication CN101010381a discloses the preparation of flame retardant injection molded articles from metal hydroxide, PLA and acrylate resins. Patent publication number CN101148498A discloses copolymerizing a phosphorus-containing component with a polyester to form a degradable flame retardant copolyester and blending with an aliphatic copolyester to achieve flame retardance of the polyester. Publication number CN101245174a discloses a method of flame retarding a blend of PBS and PLA with aluminum hydroxide. However, flame retardant modification of polyhydroxyalkanoates has been rarely studied and only a small number of documents have been reported. Publication No. CN1733828A uses synthetic method to realize flame retardance, but has the disadvantages of difficult industrialization, high cost and adverse environmental protection and human safety due to toxicity generated during bromine combustion, which is limited by European Union and other countries. Publication number CN102924888A discloses a method of flame retarding PHA from sodium hydroxide aluminum. The inorganic salt adding method is mainly adopted for flame retardance, and the ideal flame retardance effect can be obtained only by a large adding amount, so that other physical properties of the material are reduced finally. There is thus an urgent need to develop polyhydroxyalkanoate materials having good flame retardant properties and maintaining excellent material properties.
Disclosure of Invention
The invention aims to solve the problems that the synthesis process in the prior art is difficult to realize industrial production, the cost is high, the consumption of the added inorganic flame retardant is large, and the service performance of the material is reduced.
In order to achieve the purpose, the invention adopts low-dosage halogen-free environment-friendly flame retardant to prepare the degradable polyhydroxyalkanoate material with good flame retardant property and good comprehensive performance of the material, and is environment-friendly and safe.
The invention provides a flame retardant material, which comprises polyhydroxyalkanoate and a halogen-free flame retardant.
Preferably, the mass ratio of the polyhydroxyalkanoate to the halogen-free flame retardant is (2-9): 1, preferably (3-6): 1 or (4-6.5): 1. for example, the mass ratio may be (2, 2.5, 3, 3.5, 4, 4.3, 4.5, 4.8, 5, 5.5, 5.6, 5.7, 6, 6.3, 6.4, 6.5, 7, 8, 9): 1.
preferably, the halogen-free flame retardant is added in an amount of 5% -20%, preferably 9% -20%, for example 5%, 8%, 9%, 10%, 13%, 14%, 15%, 16%, 17%, 18%, 20% of the flame retardant material by mass ratio.
In one embodiment of the invention, the flame retardant material comprises 95-140 (e.g., 95, 100, 105, 110, 115, 120, 130, 135, 140) parts by weight of polyhydroxyalkanoate and 15-25 (e.g., 15, 20, 18.5, 25) parts by weight of halogen-free flame retardant.
The polyhydroxyalkanoate comprises a homopolymer or copolymer (e.g., random copolymerization and block copolymer) of monomers comprising the polyhydroxyalkanoate. Further preferred, the PHA comprises a monomer, dimer, or multimer of monomers comprising the PHA, and a material of which the monomers comprising the PHA are polymerized with other substances.
Preferably, the monomer constituting the polyhydroxyalkanoate comprises one, two or more of 2-hydroxypropionic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 3-hydroxyvaleric acid, 5-hydroxyvaleric acid, 3-hydroxycaproic acid, 3-hydroxyheptanoic acid, 3-hydroxyoctanoic acid, 3-hydroxynonanoic acid, 3-hydroxydecanoic acid, and 3-hydroxydodecanoic acid. Further preferably, the polyhydroxyalkanoate comprises one, two or more of P (HA-LA), P3HP, PHB, P4HB, PHV, PHO, PHN, PHD, PHBV, P, HB, PHBHHp, PHBHHx, P3HB4HB3HV or P3HB4HB5 HV. Wherein, in P (HA-LA), HA is selected from one, two or more than two of 3-hydroxy propionic acid, 3-hydroxy butyric acid, 4-hydroxy butyric acid, 3-hydroxy valeric acid, 5-hydroxy valeric acid, 3-hydroxy caproic acid, 3-hydroxy heptanoic acid, 3-hydroxy caprylic acid, 3-hydroxy nonanoic acid, 3-hydroxy capric acid and 3-hydroxy dodecanoic acid; LA is 2-hydroxypropionic acid.
Preferably, the polyhydroxyalkanoate can be prepared by chemical synthesis, biological fermentation, or purchased.
The molar content of 4HB in the P34HB is any value from 1% to 30%, for example 1%, 5%, 10%, 15%, 20%, 25%, 30%, preferably the molar content of 4HB in the P34HB is from 10% to 20%.
The molar content of 3HV in said PHBV is any value from 1% to 30%, for example 1%, 5%, 10%, 15%, 20%, 25%, 30%, preferably the molar content of 3HV in said PHBV is from 5% to 15%.
The molar content of HHX in PHBHHx is any value of 1% -30%, such as 1%, 5%, 10%, 15%, 20%, 25%, 30%, preferably the molar content of HHX in PHBHHx is 1% -10%.
The polyhydroxyalkanoate may be one alone or a combination of two or more thereof, as desired for the particular embodiment. For example, in one embodiment of the invention, the polyhydroxyalkanoate is 15 parts PHB and 120 parts P34HB (preferably 4HB in a molar amount of 15%). In another embodiment of the invention, the polyhydroxyalkanoate is 60 parts PHBV (preferably 3HV molar content 10%) with 60 parts PHBHHx (preferably HHHx molar content 5%). In another embodiment of the invention, the polyhydroxyalkanoate is 60 parts PHBV (preferably 3HV molar content 5%) with 60 parts P34HB (preferably HHHx molar content 25%).
The halogen-free flame retardant comprises one or two or more of silicon flame retardant, bio-based phosphorus flame retardant, bio-based polyhydroxy flame retardant and bio-based nitrogen flame retardant.
Preferably, the halogen-free flame retardant comprises a bio-based phosphorus flame retardant, a bio-based polyhydroxy flame retardant and/or a bio-based nitrogen flame retardant. Further preferably, the halogen-free flame retardant further comprises a silicon-based flame retardant.
In one embodiment of the present invention, the halogen-free flame retardant includes bio-based phosphorus flame retardant, bio-based polyhydroxy flame retardant and bio-based nitrogen flame retardant. Preferably comprises, by mass, 4.5 to 11 parts (e.g., 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11) of a bio-based phosphorus flame retardant, 3 to 6 parts (3, 3.5, 4, 4.5, 5, 5.5, 6) of a bio-based polyhydroxy flame retardant, and 3 to 6 parts (3, 3.5, 4, 4.5, 5, 5.5, 6) of a bio-based nitrogen flame retardant.
In one specific embodiment of the invention, the bio-based phosphorus flame retardant is more than the bio-based polyhydroxy flame retardant and is also more than the bio-based nitrogen flame retardant according to the parts by weight. Preferably, the sum of the addition of the bio-based polyhydroxy flame retardant and the bio-based nitrogen flame retardant is about 1.5-2.5 times of the addition of the bio-based phosphorus flame retardant.
In one embodiment of the present invention, the ratio of the bio-based phosphorus-based flame retardant, the bio-based polyhydroxy flame retardant and the bio-based nitrogen-based flame retardant may be (1.5-2.2): (0.8-1.2): (0.8-1.2).
In one embodiment of the present invention, the halogen-free flame retardant includes a silicon-based flame retardant, a bio-based phosphorus-based flame retardant, a bio-based polyhydroxy flame retardant, and a bio-based nitrogen-based flame retardant. Preferably, the flame retardant comprises, by mass, 0 to 6 parts (e.g., 0, 1, 2, 3, 3.5, 4, 4.5, 5, 5.5, 6) of a silicon-based flame retardant, 4.5 to 11 parts (e.g., 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11) of a bio-based phosphorus-based flame retardant, 3 to 6 parts (3, 3.5, 4, 4.5, 5, 5.5, 6) of a bio-based polyhydroxy flame retardant, and 3 to 6 parts (3, 3.5, 4, 4.5, 5, 5.5, 6) of a bio-based nitrogen-based flame retardant.
The bio-based phosphorus flame retardant comprises one, two or three of DOPO modified castor oil, phytic acid or sodium phytate.
The bio-based polyhydroxy flame retardant comprises one or two or more of starch, lignin, cellulose, chitosan, cyclodextrin, tannic acid and itaconic acid.
The bio-based nitrogen-based flame retardant includes, but is not limited to, urea and/or urea-melamine complex. Preferably, the urea complex melamine is urea and melamine in the following (1-3): 2 (preferably physical blending).
The silicon-based flame retardant includes, but is not limited to, one or two or more of polysilaboxane, an organosilicon-based flame retardant 3820, or a silicon-based flame retardant FCA-107, and combinations thereof.
The flame retardant material also comprises an auxiliary agent. The addition amount of the auxiliary agent is 0% -7%, preferably 0.5% -4% or 0.05% -0.1% or 0.5% -3.8% of the flame retardant material, for example 0.01%, 0.0125%, 0.015%, 0.017%, 0.02%, 0.05%, 0.1%, 0.5%, 1%, 2%, 3%, 3.8%, 4%, 5%, 6% and 7% of the flame retardant material.
In the flame retardant material, polyhydroxyalkanoate is prepared from the following components in percentage by mass: halogen-free flame retardant: auxiliary = (95-140): (15-25): (0% -7%).
The auxiliary agent comprises one or two or more of a coupling agent, a dispersing agent, a lubricant, an anti-dripping agent and an antioxidant and the combination of the two or more.
Preferably, the coupling agent includes, but is not limited to, one or two of silane coupling agent KH-792, silane coupling agent DL-602, silane coupling agent Y-5475, silane coupling agent Y-5669, titanate coupling agent TMC-201, titanate coupling agent TMC-102, titanate coupling agent TMC-311, and combinations of more thereof.
Preferably, the dispersant includes, but is not limited to, one, two or three of ethylene bis stearamide, glyceryl monostearate and glyceryl tristearate.
Preferably, the lubricant includes, but is not limited to, low molecular weight fully degradable polyesters (e.g., 2000-10000 g/mol) and/or low molecular weight PHAs (e.g., 2500-10000 g/mol).
Preferably, the anti-drip agent includes, but is not limited to, PTFE powder TRG-460 and/or PTFE powder FS-200;
preferably, the antioxidant is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and/or tris (2, 4-di-tert-butylphenyl) phosphite; more preferably, the mass ratio of the pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate to the tris (2, 4-di-tert-butylphenyl) phosphite is (2-4): 1.
in one embodiment of the invention, the flame retardant material consists of polyhydroxyalkanoate and a halogen-free flame retardant.
In another embodiment of the invention, the flame retardant material consists of polyhydroxyalkanoate, a halogen-free flame retardant and an auxiliary agent.
In one specific embodiment of the invention, the flame retardant material comprises the following components in parts by weight:
polyhydroxyalkanoate: 95-140 parts, for example 95, 100, 105, 110, 115, 120, 130, 135, 140 parts;
halogen-free flame retardant: 15-25 parts, e.g. 15, 20, 18.5, 25 parts;
coupling agent: 0.01-1 part, preferably 0.1-0.5 part, e.g. 0.01, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1;
dispersing agent: 0.01-2 parts, preferably 0.1-1.5 parts, for example 0.01, 0.1, 0.3, 0.5, 0.7, 0.8, 0.9, 1, 1.2, 1.5, 2;
and (3) a lubricant: 0.01 to 1.5 parts, preferably 0.1 to 1 part, for example 0.01, 0.1, 0.3, 0.5, 0.7, 0.9, 1, 1.5;
anti-drip agent: 0.01-1 part, preferably 0.1-0.3 part, e.g. 0.01, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1;
an antioxidant: 0.01-1 part, preferably 0.1-0.5 part, for example 0.01, 0.1, 0.2, 0.3, 0.35, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.
In one specific embodiment of the invention, the flame retardant material comprises the following components in parts by weight:
polyhydroxyalkanoate: 95-140 parts; halogen-free flame retardant: 15-25 parts of a lubricant; 0.5-2.15 parts of auxiliary agent.
In one specific embodiment of the invention, the flame retardant material comprises the following components in parts by weight:
polyhydroxyalkanoate: 95-140 parts; halogen-free flame retardant: 15-25 parts of a lubricant; coupling agent: 0.3 parts; dispersing agent: 0.8 parts; 0.5 parts of lubricant; anti-drip agent: 0.2 parts; an antioxidant: 0.3 or 0.35.
The flame retardant material can be prepared by a conventional method in the prior art.
The invention also provides a preparation method of the flame retardant material, which comprises the steps of mixing raw materials, and then carrying out melt blending extrusion in a double-screw extruder, and carrying out air cooling bracing granulation. Wherein the raw materials comprise polyhydroxyalkanoate and halogen-free flame retardant. Preferably, the composition further comprises an auxiliary agent.
Preferably, the twin-screw processing temperature is 140-160 ℃.
In one specific embodiment of the invention, the preparation method comprises the steps of weighing polyhydroxyalkanoate and halogen-free flame retardant (preferably comprising auxiliary agents) according to the mass ratio or the mass parts listed in the flame retardant materials, adding the materials into a high-speed mixer for mixing for 5-10min, discharging, putting the materials into a double-screw extruder for melt blending extrusion, and carrying out air cooling bracing granulation, wherein the processing temperature of the double screws is 140-160 ℃.
The invention also provides application of the flame retardant material in products with flame retardant property, preferably, the products comprise building materials, home textiles, aerospace, military industry, automobiles or packaging materials.
Through the technical scheme, the invention has the following advantages:
(1) The flame retardant material used in the invention is halogen-free and environment-friendly, and mainly comprises a bio-based flame retardant, so that pollution is avoided, and V-0 level flame retardance can be achieved.
(2) The invention uses various flame retardants to produce synergistic effect, in particular to the combination of biological phosphorus flame retardants, biological polyhydroxy flame retardants and biological nitrogen flame retardants, which are respectively used as acid sources, carbon sources and air sources to play a role in flame retardance. The bio-based phosphorus flame retardant contains more flame retardant elements (used as a main flame retardant), can generate a cross-linked solid substance or a charring layer with a more stable structure when heated, and can prevent the polymer from further pyrolysis on one hand and prevent the thermal decomposition products inside from entering a gas phase to participate in the combustion process on the other hand; the biological polyhydroxy fire retardant (serving as an auxiliary fire retardant) is the basis for forming a foam carbonization layer, and strengthens the thickness of the carbonization layer obtained by heating an acid source; the biological nitrogen flame retardant (serving as an auxiliary flame retardant) has the advantages that the surface carbonization layer is more porous under the air source foaming action, external heat is difficult to penetrate through the condensed phase, oxygen is prevented from entering a combustion area, gaseous or liquid products generated by degradation are prevented from overflowing the surface of the material, and the ideal flame retardant effect is achieved.
(3) The flame retardant used for preparing the flame retardant material has low consumption, can achieve ideal effect by adding a proper amount, and does not influence the service performance and other physical properties of the material.
(4) The preparation method of the invention has low cost and simple production process, and is easy for industrial production.
All combinations of items to which the term "and/or" is attached "in this description shall be taken to mean that the respective combinations have been individually listed herein. For example, "a and/or B" includes "a", "a and B", and "B". Also for example, "A, B and/or C" include "a", "B", "C", "a and B", "a and C", "B and C" and "a and B and C".
The terms "comprises" and "comprising" as used herein are intended to be inclusive and open-ended as defined by the specified components or steps described, and other specified components or steps not materially affected.
The English abbreviations and Chinese full-scale comparison of the invention are shown in Table 1.
Table 1: english abbreviation and Chinese holonomic reference
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The materials used in the examples of the present invention are commercially available unless otherwise specified.
Unless otherwise specified, parts,% or ratios described in the examples of the present invention are based on mass.
The detection criteria for the parameters in the examples are as follows:
1. tensile strength (MPa), see GB/T1040.2-2006.
2. Tensile elongation at break (%), see GB/T1040.2-2006.
3. Flexural Strength (MPa), see GB/T9341-2008.
4. Flexural modulus (MPa), see GB/T9341-2008.
5. Flame retardancy (-), see GB/T2408-2008. And (3) injection: sequencing of flame retardance: v-0 > V-1 > V-2 > HB40 > HB75.
6. The thermal deformation temperature under load is 0.45MPa (DEG C), GB/T1634-2019.
Example 1: preparation of flame-retardant PHA (PHB+P34 HB) material
120 parts of P3HB4HB (15% of 4HB mol), 15 parts of PHB, 3 parts of DOPO modified castor oil, 4.5 parts of phytic acid, 1.5 parts of lignin, 2 parts of chitosan, 4 parts of urea composite melamine, 0.15 part of silane coupling agent KH-792, 0.05 part of silane coupling agent Y-5475, 0.1 part of titanate coupling agent TMC-201, 0.5 part of ethylene bis stearamide, 0.3 part of stearic acid monoglyceride, 0.5 part of low molecular weight fully degradable polyester lubricant, 0.2 part of modified PTFE powder TRG-460, 0.2 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 0.1 part of tri (2, 4-di-tert-butylphenyl) phosphite are added into a high-speed mixer to be mixed for 5-10min, and then discharged into a twin-screw extruder to be melted, blended and extruded, and air-cooled to be pelletized. The processing temperature of the twin-screw is 140-160 ℃. The prepared flame retardant material has good flame retardant property and comprehensive performance. The specific flame retardance was V-0, and the elongation at break was 42%.
Example 2: preparation of flame-retardant PHA (P34 HB) material
140 parts by mass of P3HB4HB (12% by mole of 4 HB), 3 parts by mass of polysilaboxane, 3 parts by mass of DOPO modified castor oil, 8 parts by mass of sodium phytate, 2 parts by mass of starch, 2.5 parts by mass of lignin, 1.5 parts by mass of cellulose, 2 parts by mass of urea, 3 parts by mass of urea composite melamine, 0.1 part by mass of silane coupling agent DL-602, 0.1 part by mass of silane coupling agent Y-5475, 0.1 part by mass of titanate coupling agent TMC-102, 0.4 part by mass of ethylene bis-stearamide, 0.4 part by mass of glyceryl tristearate, 0.2 part by mass of low molecular weight fully degradable polyester lubricant, 0.3 part by mass of low molecular weight PHB, 0.2 part by mass of PTFE powder FS-200, 0.2 part by mass of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and 0.1 part by mass of tri (2, 4-di-tert-butylphenyl) phosphite are added into a high speed mixer to be mixed for 5-10min, and then placed into a twin-screw extruder to be melt-blended and extruded, granulated and bracing. The processing temperature of the twin-screw is 140-160 ℃. The prepared flame retardant material has good flame retardant property and comprehensive performance, and the results are shown in Table 3.
Example 3: preparation of flame-retardant PHA (PHB) material
95 parts of PHB, 2 parts of organic silicon fire retardant 3820, 2.5 parts of silicon flame retardant FCA-107, 4.5 parts of DOPO modified castor oil, 1.5 parts of lignin, 1.5 parts of cyclodextrin, 3 parts of urea compound melamine, 0.075 part of silane coupling agent KH-792, 0.125 part of silane coupling agent Y-5669, 0.1 part of titanate coupling agent TMC-311, 0.4 part of ethylene bis-stearamide, 0.4 part of glyceryl tristearate, 0.5 part of low molecular weight PHB, 0.1 part of modified PTFE powder TRG-460, 0.1 part of PTFE powder FS-200 and 0.3 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are added into a high-speed mixer to be mixed for 5-10min, and then the materials are put into a double-screw extruder to be melted, mixed and extruded, cooled and granulated. The processing temperature of the twin-screw is 140-160 ℃. The prepared flame retardant material has good flame retardant property and comprehensive performance.
The obtained materials were examined, and the results are shown in Table 2.
Table 2: test data for flame retardant PHA (PHB) materials
Example 4: preparation of flame-retardant PHA (PHBHHx) material
130 parts of PHBHHx (HHx molar content 10%), 3 parts of polysilaboxane, 2 parts of organic silicon fire retardant 3820, 3.5 parts of DOPO modified castor oil, 4.5 parts of phytic acid, 1.5 parts of cellulose, 1.5 parts of tannic acid, 1 part of itaconic acid, 3 parts of urea composite melamine, 0.1 part of silane coupling agent DL-602, 0.125 part of silane coupling agent Y-5669, 0.075 part of titanate coupling agent TMC-102, 0.35 part of stearic acid monoglyceride, 0.45 part of glyceryl tristearate, 0.5 part of low molecular weight fully degradable polyester lubricant, 0.2 part of modified PTFE powder TRG-460, 0.2 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 0.1 part of tri (2, 4-di-tert-butylphenyl) phosphite are added into a high-speed mixer to be mixed for 5-10min, and then discharged into a twin-screw extruder to be melted, mixed, extruded, granulated and bracing. The processing temperature of the twin-screw is 140-160 ℃. The prepared flame retardant material has good flame retardant property and comprehensive performance, and the flame retardance is V-0.
Example 5: preparation of flame-retardant PHA (PHBHHx+PHBV) material
60 parts of PHBHHx (HHx molar content 5%), 60 parts of PHBV (3 HV molar content 10%), 2.5 parts of DOPO modified castor oil, 4 parts of phytic acid, 2.5 parts of sodium phytate, 1 part of cellulose, 1 part of cyclodextrin, 1.5 parts of tannic acid, 2 parts of urea, 4 parts of urea composite melamine, 0.15 part of silane coupling agent Y-5669, 0.075 part of titanate coupling agent TMC-102, 0.075 part of titanate coupling agent TMC-311, 0.5 part of ethylene bis stearamide, 0.3 part of stearic acid monoglyceride, 0.2 part of low molecular weight fully degradable polyester lubricant, 0.3 part of low molecular weight PHB, 0.2 part of PTFE powder FS-200, 0.2 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 0.1 part of tri (2, 4-di-tert-butylphenyl) phosphite are added into a high-speed mixer to be mixed for 5-10min, and then put into a twin-screw extruder to be extruded, pelletized, extruded into a cold extruder, and extruded. The processing temperature of the twin-screw is 140-160 ℃. The prepared flame retardant material has good flame retardant property and comprehensive performance, and the flame retardance is V-0.
Example 6: preparation of flame-retardant PHA (P34 HB+PHBV) material
60 parts by mass of P3HB4HB (25% by mole of 4 HB), 60 parts by mass of PHBV (5% by mole of 3 HV), 2 parts by mass of polysilaboxane, 3.5 parts by mass of silicone flame retardant FCA-107, 4 parts by mass of DOPO modified castor oil, 6 parts by mass of sodium phytate, 2 parts by mass of lignin, 2 parts by mass of chitosan, 1.5 parts by mass of itaconic acid, 4 parts by mass of urea composite melamine, 0.15 part by mass of silane coupling agent KH-792, 0.05 part by mass of silane coupling agent Y-5475, 0.1 part by mass of titanate coupling agent TMC-201, 0.35 part by mass of glycerol monostearate, 0.45 part by mass of glycerol tristearate, 0.5 part by mass of low molecular weight PHB, 0.1 part by mass of modified PTFE powder TRG-460, 0.1 part by mass of PTFE powder FS-200, 0.35 part by mass of tri (2, 4-di-tert-butylphenyl) phosphite are added into a high-speed mixer, mixed for 5-10min, and then fed into a twin-screw extruder for melt blending and extrusion, air-cooling and granulating. The processing temperature of the twin-screw is 140-160 ℃. The prepared flame retardant material has good flame retardant property and comprehensive performance, and the flame retardance is V-0.
Example 7: preparation of flame-retardant PHA (P34 HB) material
140 parts of P3HB4HB (4 HB mol content 12%), 3 parts of polysilaboxane, 3 parts of DOPO modified castor oil, 8 parts of sodium phytate, 2 parts of starch, 2.5 parts of lignin, 1.5 parts of cellulose, 2 parts of urea and 3 parts of urea composite melamine are added into a high-speed mixer to be mixed for 5-10min, and then discharged and fed into a double-screw extruder to be melted, blended and extruded, and air-cooled to form bracing granules. The processing temperature of the twin-screw is 140-160 ℃. The prepared flame retardant material has good flame retardant property and comprehensive performance, the flame retardant property is V-0, and the load heat distortion temperature is 0.45MPa and is 104 ℃.
Comparative example 1: preparation of flame-retardant PHA (P34 HB) material with excessive addition of flame retardant
140 parts by mass of P3HB4HB (12% by mole of 4 HB), 5 parts by mass of polysilaboxane, 5 parts by mass of DOPO modified castor oil, 12 parts by mass of sodium phytate, 4 parts by mass of starch, 3.5 parts by mass of lignin, 2.5 parts by mass of cellulose, 3 parts by mass of urea, 5 parts by mass of urea composite melamine, 0.1 part by mass of silane coupling agent DL-602, 0.1 part by mass of silane coupling agent Y-5475, 0.1 part by mass of titanate coupling agent TMC-102, 0.4 part by mass of ethylene bis-stearamide, 0.4 part by mass of glyceryl tristearate, 0.2 part by mass of low molecular weight fully degradable polyester lubricant, 0.3 part by mass of low molecular weight PHB, 0.2 part by mass of PTFE powder FS-200, 0.2 part by mass of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and 0.1 part by mass of tri (2, 4-di-tert-butylphenyl) phosphite are added into a high speed mixer to be mixed for 5-10min, and then placed into a twin-screw extruder to be melt-blended and extruded, granulated and bracing. The processing temperature of the twin-screw is 140-160 ℃. The flame retardant property and the comprehensive property of the prepared flame retardant material are shown in Table 3.
Comparative example 2: preparation of flame retardant type-changeable flame-retardant PHA (P34 HB) material
140 parts by mass of P3HB4HB (12% of 4HB mole content), 7 parts by mass of boron oxide, 18 parts by mass of magnesium hydroxide flame retardant, 0.1 part by mass of silane coupling agent DL-602, 0.1 part by mass of silane coupling agent Y-5475, 0.1 part by mass of titanate coupling agent TMC-102, 0.4 part by mass of ethylene bis stearamide, 0.4 part by mass of glyceryl tristearate, 0.2 part by mass of low molecular weight fully degradable polyester lubricant, 0.3 part by mass of low molecular weight PHB, 0.2 part by mass of PTFE powder FS-200, 0.2 part by mass of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 0.1 part by mass of tri (2, 4-di-tert-butylphenyl) phosphite are added into a high-speed mixer to be mixed for 5-10min, and then discharged materials are put into a twin-screw extruder to be melt blended and extruded, and air cooled to be subjected to bracing granulation. The processing temperature of the twin-screw is 140-160 ℃. The flame retardant property and the comprehensive property of the prepared flame retardant material are shown in Table 3.
Comparative example 3: preparation of PHA (P34 HB) material without biobased phosphorus flame retardant, and supplementing the balance with other types of flame retardants
140 parts by mass of P3HB4HB (12% by mole of 4 HB), 5 parts by mass of polysilaboxane, 3.5 parts by mass of starch, 4 parts by mass of lignin, 2.5 parts by mass of cellulose, 4 parts by mass of urea, 6 parts by mass of urea composite melamine, 0.1 part by mass of silane coupling agent DL-602, 0.1 part by mass of silane coupling agent Y-5475, 0.1 part by mass of titanate coupling agent TMC-102, 0.4 part by mass of ethylene bis stearamide, 0.4 part by mass of glyceryl tristearate, 0.2 part by mass of low molecular weight fully degradable polyester lubricant, 0.3 part by mass of low molecular weight PHB, 0.2 part by mass of PTFE powder FS-200, 0.2 part by mass of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and 0.1 part by mass of tri (2, 4-di-tert-butylphenyl) phosphite are added into a high-speed mixer to be mixed for 5-10min, and then discharged and put into a twin-screw extruder to be melt, blended, extruded and air-cooled to be pelletized. The processing temperature of the twin-screw is 140-160 ℃. The flame retardant property and the comprehensive property of the prepared flame retardant material are shown in Table 3.
Comparative example 4: preparation of PHA (P34 HB) material free of biopolyhydroxy flame retardant, the balance being supplemented with other types of flame retardants
140 parts by mass of P3HB4HB (12% by mole of 4 HB), 4 parts by mass of polysilaboxane, 4 parts by mass of DOPO modified castor oil, 10.5 parts by mass of sodium phytate, 2.5 parts by mass of urea, 4 parts by mass of urea composite melamine, 0.1 part by mass of silane coupling agent DL-602, 0.1 part by mass of silane coupling agent Y-5475, 0.1 part by mass of titanate coupling agent TMC-102, 0.4 part by mass of ethylene bis stearamide, 0.4 part by mass of glyceryl tristearate, 0.2 part by mass of low molecular weight fully degradable polyester lubricant, 0.3 part by mass of low molecular weight PHB, 0.2 part by mass of PTFE powder FS-200, 0.2 part by mass of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and 0.1 part by mass of tri (2, 4-di-tert-butylphenyl) phosphite are added into a high-speed mixer to be mixed for 5-10min, and then discharged and put into a twin-screw extruder to be melt, blended, extruded and air-cooled to be pelletized. The processing temperature of the twin-screw is 140-160 ℃. The flame retardant property and the comprehensive property of the prepared flame retardant material are shown in Table 3.
Comparative example 5: preparation of PHA (P34 HB) material without biobased nitrogen flame retardant, and supplementing the balance with other types of flame retardants
140 parts by mass of P3HB4HB (12% by mole of 4 HB), 4 parts by mass of polysilaboxane, 4 parts by mass of DOPO modified castor oil, 10 parts by mass of sodium phytate, 2.5 parts by mass of starch, 3 parts by mass of lignin, 1.5 parts by mass of cellulose, 0.1 part by mass of a silane coupling agent DL-602, 0.1 part by mass of a silane coupling agent Y-5475, 0.1 part by mass of a titanate coupling agent TMC-102, 0.4 part by mass of ethylene bis stearamide, 0.4 part by mass of glycerol tristearate, 0.2 part by mass of a low molecular weight fully degradable polyester lubricant, 0.3 part by mass of low molecular weight PHB, 0.2 part by mass of PTFE powder FS-200, 0.2 part by mass of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and 0.1 part by mass of tri (2, 4-di-tert-butylphenyl) phosphite are added into a high-speed mixer to be mixed for 5-10min, and then fed into a twin-screw extruder for melt, extrusion, air cooling and strand granulation. The processing temperature of the twin-screw is 140-160 ℃. The flame retardant property and the comprehensive property of the prepared flame retardant material are shown in Table 3.
Comparative example 6: preparation of PHA (P34 HB) material without biobased phosphorus and nitrogen flame retardant, and supplementing the balance with other flame retardants
140 parts by mass of P3HB4HB (12% by mole of 4 HB), 7 parts by mass of polysilaboxane, 6 parts by mass of starch, 6.5 parts by mass of lignin, 5.5 parts by mass of cellulose, 0.1 part by mass of silane coupling agent DL-602, 0.1 part by mass of silane coupling agent Y-5475, 0.1 part by mass of titanate coupling agent TMC-102, 0.4 part by mass of ethylene bis stearamide, 0.4 part by mass of glyceryl tristearate, 0.2 part by mass of low molecular weight fully degradable polyester lubricant, 0.3 part by mass of low molecular weight PHB, 0.2 part by mass of PTFE powder FS-200, 0.2 part by mass of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester and 0.1 part by mass of tri (2, 4-di-tert-butylphenyl) phosphite are added into a high speed mixer to be mixed for 5-10min, and then the materials are put into a twin-screw extruder to be melted, blended and extruded, and subjected to air cooling bracing granulation. The processing temperature of the twin-screw is 140-160 ℃. The flame retardant property and the comprehensive property of the prepared flame retardant material are shown in Table 3.
Comparative example 7: preparation of PHA (P34 HB) material without biobased phosphorus and polyhydroxy flame retardant, and supplementing the balance with other types of flame retardants
140 parts by mass of P3HB4HB (12% of 4HB molar content), 9 parts by mass of polysilaboxane, 7 parts by mass of urea, 9 parts by mass of urea composite melamine, 0.1 part by mass of silane coupling agent DL-602, 0.1 part by mass of silane coupling agent Y-5475, 0.1 part by mass of titanate coupling agent TMC-102, 0.4 part by mass of ethylene bis stearamide, 0.4 part by mass of glyceryl tristearate, 0.2 part by mass of low molecular weight fully degradable polyester lubricant, 0.3 part by mass of low molecular weight PHB, 0.2 part by mass of PTFE powder FS-200, 0.2 part by mass of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester and 0.1 part by mass of tri (2, 4-di-tert-butylphenyl) phosphite are added into a high-speed mixer to be mixed for 5-10min, and then discharged into a double screw extruder to be subjected to melt, blended, extruded, and subjected to air cooling bracing granulation. The processing temperature of the twin-screw is 140-160 ℃. The flame retardant property and the comprehensive property of the prepared flame retardant material are shown in Table 3.
Comparative example 8: preparation of PHA (P34 HB) material without biological polyhydroxy and nitrogen flame retardant, and supplementing the balance with other flame retardants
140 parts by mass of P3HB4HB (12% of 4HB molar content), 5 parts by mass of polysilaboxane, 5 parts by mass of DOPO modified castor oil, 15 parts by mass of sodium phytate, 0.1 part by mass of silane coupling agent DL-602, 0.1 part by mass of silane coupling agent Y-5475, 0.1 part by mass of titanate coupling agent TMC-102, 0.4 part by mass of ethylene bis stearamide, 0.4 part by mass of glyceryl tristearate, 0.2 part by mass of low molecular weight fully degradable polyester lubricant, 0.3 part by mass of low molecular weight PHB, 0.2 part by mass of PTFE powder FS-200, 0.2 part by mass of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 0.1 part by mass of tri (2, 4-di-tert-butylphenyl) phosphite are added into a high-speed mixer to be mixed for 5-10min, and then the materials are put into a twin-screw extruder to be melted, blended and extruded, and subjected to air cooling bracing granulation. The processing temperature of the twin-screw is 140-160 ℃. The flame retardant property and the comprehensive property of the prepared flame retardant material are shown in Table 3.
Comparative example 9: preparation of flame-retardant PHA (P34 HB) material with other proportions
140 parts by mass of P3HB4HB (12% by mole of 4 HB), 3 parts by mass of polysilaboxane, 2 parts by mass of DOPO modified castor oil, 3 parts by mass of sodium phytate, 2 parts by mass of starch, 1.5 parts by mass of lignin, 2.5 parts by mass of cellulose, 4 parts by mass of urea, 7 parts by mass of urea composite melamine, 0.1 part by mass of silane coupling agent DL-602, 0.1 part by mass of silane coupling agent Y-5475, 0.1 part by mass of titanate coupling agent TMC-102, 0.4 part by mass of ethylene bis-stearamide, 0.4 part by mass of glyceryl tristearate, 0.2 part by mass of low molecular weight fully degradable polyester lubricant, 0.3 part by mass of low molecular weight PHB, 0.2 part by mass of PTFE powder FS-200, 0.2 part by mass of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and 0.1 part by mass of tri (2, 4-di-tert-butylphenyl) phosphite are added into a high speed mixer to be mixed for 5-10min, and then placed into a twin-screw extruder to be melt-blended and extruded, granulated and bracing. The processing temperature of the twin-screw is 140-160 ℃. The flame retardant property and the comprehensive property of the prepared flame retardant material are shown in Table 3. The results of experiments in example 2 and comparative examples 1 to 9 are summarized in Table 3.
Table 3: test data for example 2, comparative examples 1-9
As can be seen from the results of tables 1 to 3, in examples 1 to 7 of the flame retardant polyhydroxyalkanoate prepared by the method of the present invention, the flame retardant effect of the material prepared as a result of the specific components and the specific combined contents of the present invention is good, and the properties are excellent, particularly in terms of tensile strength, elongation at break, flexural strength, flexural modulus, etc., and the cost of the present invention is low, the production process is simple, and the present invention is easy for industrial production.
Compared with the embodiment 2, the embodiment 1 improves the addition amount of the flame retardant, and the comprehensive performance of the material is affected.
Comparative example 2 has a flame retardant type changed compared with example 2, and has a reduced flame retardant property, a reduced bio-based component of the material, an affected overall property and an inferior effect.
Comparative examples 3 to 8 compared with example 2, flame retardant properties were greatly lowered and the overall properties of the materials were affected due to the lack of a synergistic effect between the bio-based phosphorus flame retardant, the bio-based polyhydroxy flame retardant and the bio-based nitrogen flame retardant.
Comparative example 9 compared with example 2, the halogen-free flame retardant has too little bio-based phosphorus flame retardant, too much bio-based nitrogen flame retardant, and inconsistent proportion, and the comprehensive performance of the material is affected.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. The flame retardant material is characterized by comprising polyhydroxyalkanoate and a halogen-free flame retardant, wherein the halogen-free flame retardant comprises a bio-based phosphorus flame retardant, a bio-based polyhydroxyalkanoate and a bio-based nitrogen flame retardant;
the polyhydroxyalkanoate comprises a homopolymer or copolymer of monomers constituting the polyhydroxyalkanoate,
wherein the monomer for forming the polyhydroxyalkanoate comprises one, two or more than two of 2-hydroxy propionic acid, 3-hydroxy butyric acid, 4-hydroxy butyric acid, 3-hydroxy valeric acid, 5-hydroxy valeric acid, 3-hydroxy caproic acid, 3-hydroxy heptanoic acid, 3-hydroxy caprylic acid, 3-hydroxy nonanoic acid, 3-hydroxy capric acid and 3-hydroxy dodecanoic acid;
the bio-based phosphorus flame retardant is one, two or three of DOPO modified castor oil, phytic acid or sodium phytate;
the biological polyhydroxy fire retardant is one or two or more selected from starch, lignin, cellulose, chitosan, cyclodextrin, tannic acid or itaconic acid;
the bio-based nitrogen flame retardant is selected from urea and/or urea composite melamine.
2. The flame retardant material according to claim 1, wherein the mass ratio of the polyhydroxyalkanoate to the halogen-free flame retardant is (2-9): 1.
3. the flame retardant material of claim 1, wherein the polyhydroxyalkanoate comprises one, two or more of P (HA-LA), P3HP, PHB, P4HB, PHV, PHO, PHN, PHD, PHBV, P34HB, PHBHHp, PHBHHx, P HB3HV or P3HB4HB5 HV;
wherein, in P (HA-LA), HA is selected from one, two or more than two of 3-hydroxy propionic acid, 3-hydroxy butyric acid, 4-hydroxy butyric acid, 3-hydroxy valeric acid, 5-hydroxy valeric acid, 3-hydroxy caproic acid, 3-hydroxy heptanoic acid, 3-hydroxy caprylic acid, 3-hydroxy nonanoic acid, 3-hydroxy capric acid and 3-hydroxy dodecanoic acid; LA is 2-hydroxypropionic acid.
4. The flame retardant material of claim 1, wherein the halogen-free flame retardant comprises 4.5-11 parts of bio-based phosphorus flame retardant, 3-6 parts of bio-based polyhydroxy flame retardant and 3-6 parts of bio-based nitrogen flame retardant.
5. The flame retardant material of claim 1, wherein the halogen-free flame retardant further comprises a silicon-based flame retardant selected from one or a combination of two or more of polysilaboxane, a silicone-based flame retardant 3820, or a silicon-based flame retardant FCA-107.
6. The flame retardant material of claim 1, further comprising an auxiliary agent, wherein the auxiliary agent comprises one or a combination of two or more of a coupling agent, a dispersing agent, a lubricant, an anti-dripping agent, and an antioxidant.
7. The flame retardant material of claim 6, wherein,
the coupling agent is one or two or more of silane coupling agent KH-792, silane coupling agent DL-602, silane coupling agent Y-5475, silane coupling agent Y-5669, titanate coupling agent TMC-201, titanate coupling agent TMC-102 and titanate coupling agent TMC-311;
the dispersing agent is selected from one, two or three of ethylene bis stearamide, stearic acid monoglyceride and tristearin;
the lubricant is selected from low molecular weight fully degradable polyesters and/or low molecular weight PHAs;
the anti-dripping agent is selected from PTFE powder TRG-460 and/or PTFE powder FS-200;
the antioxidant is pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and/or tri (2, 4-di-tert-butylphenyl) phosphite.
8. The flame retardant material of any of claims 1-7, wherein the flame retardant material comprises, in parts by weight:
polyhydroxyalkanoate: 95-140 parts;
halogen-free flame retardant: 15-25 parts of a lubricant;
coupling agent: 0.01-1 part;
dispersing agent: 0.01-2 parts;
and (3) a lubricant: 0.01-1.5 parts;
anti-drip agent: 0.01-1 part;
an antioxidant: 0.01-1 part.
9. A method for preparing a flame retardant material according to any one of claims 1 to 8, comprising mixing raw materials, then melt blending and extruding in a twin screw extruder, and granulating by air cooling and bracing, wherein the raw materials comprise polyhydroxyalkanoate and halogen-free flame retardant.
10. Use of a fire retardant material according to any one of claims 1 to 8 in a product requiring fire retardant properties of the material, wherein the product comprises a building material, a home textile, an aerospace, a military, an automotive or packaging material.
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