CN114773776A - Halogen-free flame-retardant polyformaldehyde granules and production process thereof - Google Patents
Halogen-free flame-retardant polyformaldehyde granules and production process thereof Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K13/02—Organic and inorganic ingredients
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
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- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/43—Compounds containing sulfur bound to nitrogen
- C08K5/435—Sulfonamides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/529—Esters containing heterocyclic rings not representing cyclic esters of phosphoric or phosphorous acids
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- C—CHEMISTRY; METALLURGY
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- 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
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Abstract
The invention provides a halogen-free flame-retardant polyformaldehyde granule and a production process thereof, belonging to the technical field of flame-retardant polyformaldehyde materials, wherein magnesium hydroxide is blended through lime nitrogen, the water content in a mixed material is reduced, the relative release amount of formaldehyde is reduced, non-combustible water vapor, carbon dioxide and the like are increased, the combustion of polyformaldehyde is slowed down, triethanolamine is added to stabilize the molecular chain terminal, the molecular weight terminal is inactivated, and the formaldehyde decomposition and release are reduced, a compound intumescent flame retardant system taking melamine polyphosphate, sodium aluminum basic carbonate and a phosphorus-nitrogen flame retardant as main bodies is designed, a nitrogen-phosphorus synergistic compound intumescent flame retardant system and a synergistic char forming agent system are used for matching with a formaldehyde absorption and stabilization system, the flame-retardant performance can reach UL 94-0 level, the raw materials are easy to obtain, the cost is lower, and the halogen-free flame-retardant polyformaldehyde granule has a certain economic added value, the flame-retardant polyformaldehyde zipper can be applied to flame-retardant polyformaldehyde accessories in the fields of fire fighting, petrifaction, metallurgy and the like, such as the use of a flame-retardant zipper in flame-retardant clothing.
Description
Technical Field
The invention belongs to the technical field of flame-retardant polyformaldehyde materials, and particularly relates to a production process of halogen-free flame-retardant polyformaldehyde granules.
Background
The zipper produced by taking the polyformaldehyde as the zipper teeth has higher quality and is called as a novel plastic steel zipper. Polyformaldehyde has excellent self-lubricating property and wear resistance, and a zipper made of the polyformaldehyde has good service performance. The development of halogen-based flame retardants is greatly limited due to the effects of decabromodiphenyl ether and hexabromocyclododecane, which are included as persistent organic pollutants. Halogen-free, low-smoke and low-toxicity environment-friendly engineering plastic products are always the pursued targets. Polyformaldehyde is an engineering plastic with excellent comprehensive performance and has wide application in the aspects of electronics, electric appliances, automobiles and the like. With the increasing use of polyoxymethylenes, the requirements for flame retardancy are becoming stronger. Because POM is a high molecular material which is extremely easy to burn, the oxygen index is the lowest in all polymer materials, and because the POM has strict requirements on flame retardants in the forming process, a small amount of flame retardants can decompose to cause large amount of decomposition of the POM materials. In addition, since polyoxymethylene is a polymer with high crystallinity, and the physical and mechanical properties, especially the weak notch impact resistance, may be greatly reduced by adding a large amount of additives or other high molecular materials to blend, the flame retardancy of POM is very difficult. For example, in the Chinese patent CN201810669351.X, the flame-retardant durable polyformaldehyde plastic utilizes antimony trioxide to resist flame, and the flame-retardant effect is poor. The same applies to CN109206838A and CN 103540098A. It is believed that the faster burning of POM when conventional flame retardants, such as tris (. alpha. -chloropropyl) phosphate, dichloropropyl-dihydrogen phosphate or chlorinated paraffin compounded with antimony trioxide, are added to POM is caused by decomposition of POM catalyzed by phosphoric acid or halogen groups to release free formaldehyde via the "zipper" effect. This free formaldehyde is highly flammable and can disrupt the balance of the flame self-extinguishing reaction caused by the flame retardant. For example, CN102924862A prepared a modified material containing chlorinated paraffin, tris (chloroisopropyl) phosphate, etc., and the actual flame retardant effect was not good. Strongly basic compounds can also promote formaldehyde evolution by cleaving the acyl end groups of the POM chain. The special molecular chain structure of the polyformaldehyde resin causes that a large amount of formaldehyde gas is generated in the combustion process to support combustion and form carbon, and is one of the most difficult flame-retardant high polymer materials. Therefore, those skilled in the art need to develop a new method to overcome the shortcomings of the prior art, and further meet the market demand and performance requirement.
Disclosure of Invention
In view of the defects of the prior art, the invention mainly aims to provide the halogen-free flame-retardant polyformaldehyde granules and the production process thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the halogen-free flame-retardant polyformaldehyde granule is characterized by comprising 15-20% of magnesium hydroxide and further comprising polyformaldehyde: 57-63.5% and melamine polyphosphate: 6-10% of basic sodium aluminum carbonate: 4-7% of a processing aid: 0.5 to 1.5 percent of phosphorus-nitrogen flame retardant, and the balance of phosphorus-nitrogen flame retardant, wherein the total weight of the components is 80 to 85 percent; the production process of the halogen-free flame-retardant polyformaldehyde granules comprises the following steps: (1) uniformly mixing magnesium hydroxide, the polyformaldehyde, the melamine polyphosphate, the phosphorus-nitrogen flame retardant, the basic aluminum sodium carbonate and the processing aid; (2) adding the mixture into an extruder for extrusion, uniformly adding triethanolamine, cooling and granulating to obtain the halogen-free flame-retardant polyformaldehyde granules.
When the polyoxymethylene particles are adsorbed with water, it is preferable to dry them from the viewpoint of improving the appearance of the product. When the water absorption capacity of the material is more than 0.25 percent, pre-drying is needed. As a flame retardant, magnesium hydroxide has similar characteristics to aluminum hydroxide, but has better smoke suppression effect compared with similar inorganic flame retardants, and the magnesium hydroxide produced by a chemical synthesis method or a physical method needs drying, industrial powdery magnesium hydroxide has the water content of not more than 3 percent, and the magnesium hydroxide is used as the flame retardant in polyformaldehyde, and is dried before extrusion granulation or polyformaldehyde granules are dried.
Furthermore, the magnesium hydroxide contains 5-10 wt% of lime nitrogen.
Lime nitrogen is almost only used as an ammonia fertilizer in agriculture, so that the cost is low, the price is low, and a proper amount of lime nitrogen and magnesium hydroxide are mixed in the process:
proper amount of lime nitrogen reacts with water in magnesium hydroxide to produce calcium hydroxide and cyanamide, and in alkaline magnesium hydroxide, the cyanamide may be further polymerized to form dicyandiamide.
The above reaction scheme is as follows:
the product produced by the reaction absorbs free formaldehyde when being granulated in the production of polyformaldehyde. And simultaneously used as an aldehyde absorbing agent for formaldehyde volatilization during flame retardance.
Further, the polyformaldehyde is one of homo-formaldehyde or co-formaldehyde.
Further, the processing aid is one or more of an antioxidant 2246, UV-531 or an antioxidant BHT.
Further, the phosphorus-nitrogen flame retardant is at least one of guanidine sulfamate, diammonium hydrogen phosphate and hexaphenoxycyclotriphosphazene.
Further, the triethanolamine in the step (2) is added in the 3 rd section of the machine barrel, wherein the adding amount of the triethanolamine is 0.05-0.1 wt% of the halogen-free flame-retardant polyformaldehyde granules.
The decomposition activity of polyformaldehyde can be reduced by adding triethanolamine;
further, the mixing in the step (2) is to mix materials by adopting a high-speed mixer set, the materials are stirred for 30-40 min at the temperature of 50 ℃ and 300rpm, and the extrusion temperature is as follows: the first to the fifth sections are respectively 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃ and 180 ℃ of the head temperature.
Magnesium hydroxide and basic sodium aluminum carbonate are used to provide hydroxyl conditions, improve the pH environment, and react with formaldehyde generated when combustion occurs to form an absorption effect.
The invention has the beneficial effects that:
the invention adopts lime nitrogen to mix with magnesium hydroxide, reduces the water content in the mixed material, can absorb part of water of magnesium hydroxide and polyformaldehyde, improves the drying effect, has high decomposition temperature of generated dicyandiamide, reduces the side effect of flame retardance of a zipper by using a competitive reaction in the cracking process of polyformaldehyde by improving the cracking process of polyformaldehyde, increases the content of nonflammable carbon dioxide, water vapor and an isolation carbon layer, reduces the heat transfer rate of solid polyformaldehyde, thereby also reducing the generation of volatile combustible products such as combustible formaldehyde by cracking more polymers.
Compared with the prior art, the invention has the following advantages:
the invention starts from the bad conditions that the existing polyformaldehyde has poor flame retardant property and formaldehyde volatilizes to promote combustion in combustion, realizes the good halogen-free flame retardant effect of polyformaldehyde through blending modification, develops lime nitrogen blended magnesium hydroxide, reduces the relative amount of formaldehyde release, increases non-combustible steam, carbon dioxide and the like through polymerizing flame retardant dicyandiamide formaldehyde resin, slows down the combustion of polyformaldehyde, inactivates the molecular weight end through adding triethanolamine and introducing a molecular chain end stabilizer, reduces formaldehyde decomposition and release, designs a compound intumescent flame retardant system taking melamine polyphosphate, basic aluminum sodium carbonate and phosphorus-nitrogen flame retardant as main bodies, develops halogen-free flame retardant polyformaldehyde granules through a nitrogen-phosphorus synergistic compound intumescent flame retardant system and a synergistic char-forming system and simultaneously matching a formaldehyde absorbent and a heat stabilizer system, the halogen-free flame-retardant POM modified material prepared by the process method has the flame retardant property reaching UL94-V0 level, meets the application requirements of the flame-retardant protective polyformaldehyde zipper of protective clothing, has easily obtained lime nitrogen and other flame retardant raw materials and lower cost, has certain economic added value, can be applied to flame-retardant polyformaldehyde accessories in the fields of fire fighting, petrifaction, metallurgy and the like, and can be used for fireproof zippers in fireproof flame-retardant clothing.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
The method comprises the following steps of firstly, mixing lime nitrogen and magnesium hydroxide, wherein the lime nitrogen accounts for 10wt% of weight of magnesium hydroxide in TY-250 Yuejiang, with the extruder rotating speed of 60rpm, a 300-type gantry granulator and the water temperature of a water tank of 16 ℃, and obtaining 15 parts of magnesium hydroxide, wherein the lime nitrogen is lime nitrogen powder purchased from Yixin fertilizers of Nanjing grass; secondly, selecting FORMOCON FM090 copolymerized polyformaldehyde granules according to parts by weight, and then mixing polyformaldehyde: 63.5 parts of Weifang Weidong chemical FR-NP polyphosphoric acid melamine: 6 parts of basic sodium aluminum carbonate, 4 parts of processing aid: 1.5 parts of antioxidant 2246 and 0.75 part of UV-531 as processing aids, and 10 parts of the rest phosphorus-nitrogen flame retardant, wherein the total amount of the components is 85 parts; step three, mixing materials: mixing weighed magnesium hydroxide, polyformaldehyde, melamine polyphosphate, phosphorus-nitrogen flame retardant, basic sodium aluminum carbonate and processing aid by using a high-speed mixing unit, stirring for 340min at the temperature of 50 ℃ and at the speed of 300rpm, and uniformly mixing, wherein the phosphorus-nitrogen flame retardant is a mixture of guanidine sulfamate and diammonium hydrogen phosphate in a mass ratio of 1: 1, and guanidine sulfamate is produced in a Hebei Nanbao tripod chemical industry; (2) adding the mixture into a Keruite Machinery KRT-SJP-130-A120 granulation line extruder, extruding and uniformly filling triethanolamine at the temperature of 140-170 ℃, wherein the triethanolamine filling is filling in the 3 rd section of the extruder, the filling amount of the triethanolamine is 0.05 wt% of the halogen-free flame-retardant polyformaldehyde granules, cooling and granulating, and the extrusion temperature is as follows: the first to the fifth sections are respectively 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃ and 180 ℃ of the head temperature, and the halogen-free flame-retardant polyformaldehyde granules are obtained and marked as # 1.
Comparative example 1
The first step of example 1 was carried out using magnesium hydroxide from which lime nitrogen was removed and which contained only equal amounts of magnesium hydroxide and processing aid, and the remaining steps were identical.
Example 2
The method comprises the following steps of firstly, mixing lime nitrogen accounting for 5wt% of magnesium hydroxide in TY-250 of Yuejiang with magnesium hydroxide according to parts by weight to obtain 20 parts of magnesium hydroxide, wherein the lime nitrogen is lime nitrogen powder purchased from Yixin fertilizer of Nanjing grass; secondly, selecting polyformaldehyde M90LV DURACON polyformaldehyde according to parts by weight: 57 parts of melamine polyphosphate: 10 parts of basic sodium aluminum carbonate, 7 parts of processing aid: 0.5 part of antioxidant BHT, 0.5 part of processing aid and 5.5 parts of phosphorus-nitrogen flame retardant in balance, wherein the total amount of the components is 80 parts; step three, mixing materials: mixing weighed magnesium hydroxide, polyformaldehyde, KEMI KM-C04 melamine polyphosphate, phosphorus-nitrogen flame retardant, basic sodium aluminum carbonate and processing aid by a high-speed mixing unit, stirring for 40min at the temperature of 50 ℃ and at the speed of 300rpm, and uniformly mixing, wherein the phosphorus-nitrogen flame retardant is a mixture of SPB-100 hexaphenoxycyclotriphosphazene and guanidine sulfamate according to the mass ratio of 1: 1, and guanidine sulfamate is produced by Hebei Nanbao tripod chemical industry; (2) adding the mixture into an extruder of a KRT-SJP-130-A120 granulation line to extrude and evenly add triethanolamine, wherein the adding amount of the triethanolamine is 0.1 wt% of the halogen-free flame-retardant polyformaldehyde granules, cooling and granulating, and the extruding temperature is as follows: the temperature of the first to fifth sections is 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃ and 180 ℃ of the head, and the halogen-free flame-retardant polyformaldehyde granules are obtained and marked as # 2.
Example 3
The copolyformaldehyde of example 2 was replaced with dupont homo-polymer Delrin900P polyoxymethylene, and the remaining steps were the same as in example 2 and labeled as # 3.
The halogen-free flame-retardant polyformaldehyde granules prepared in the examples 1-3 and the comparative example 1 are subjected to performance test, and the test results are shown in Table 1
TABLE 1 Performance test results of halogen-free flame-retardant polyoxymethylene pellets of examples 1 to 3 and comparative example 1
| Item | Comparative example 1 | Example 1/1# | Example 2/2# | Example 3/3# |
| Bending strength MPa | 83 | 53.4 | 51.2 | 62.7 |
| Tensile strength MPa | 59.4 | 32.5 | 33.4 | 44.2 |
| Impact strength KJ/m of simply supported beam gap2 | 5.2 | 3.5 | 3.6 | 5.1 |
| Melt mass flow rate g/10min | 8.4 | 3.8 | 3.9 | 8.7 |
| Flame retardancy | HB | V-0 | V-0 | V-0 |
| Thermal stability 5min260 deg.C | Partial melting | No melting and no charring | No melting and no charring | No melting and no charring |
Note: sample preparation and performance determination references: specifically, the melt temperature is 205 ℃, the mold temperature is 90 ℃, and the average injection rate is 200mm s-1Preparation of injection moulded test specimens with the plastic thermoplastic material GB/T17037.1-2019 part 1: general principles and preparation of multipurpose specimens and elongated specimens type a molds were prepared to meet GB/T1040.2-2006 determination of tensile properties of plastics part 2: type 1A specimens, type B molds 80mm by 10mm by 4mm specimens in the test conditions for molding and extruding plastics; preparing a sample of 60mm multiplied by 2mm by a die of D2 type in GB/T17037.4-2003 measurement; the sample for measuring the flame retardance adopts a mould which is in accordance with the standard of GB/T2408-2021 for measuring the combustion performance of plastics to prepare a sample of 125mm multiplied by 13mm multiplied by 3mm by injection moulding; the state regulation of the sample and the state regulation of the standard environment sample of the test are carried out according to the regulation of GB/T2918, the condition of the state regulation is that the temperature is 23 ℃, the relative humidity is 50 percent, and the time is 16 h; density: the sample state is adjusted, the test is carried out according to the regulation of GB/T1033.1-2008, and the method A is adopted. Melt mass flow Rate part 1 as determined in GB/T3682.1-2018 thermoplastic melt Mass Flow Rate (MFR) and melt volume flow Rate (MVR): test methods of the Standard method, the test was carried out at 190 ℃ under a load of 2.16 kg; the bending strength test piece was 80 mm. times.10 mm. times.4 mm,after the state of the sample is adjusted, the test is carried out according to the specification of the measurement of the bending property of the GB/T9341-2008 plastic, and the test speed is 2 mm/min; the impact strength sample of the simply supported beam notch is a sample of 80mm multiplied by 10mm multiplied by 4 mm; the state of the test piece is adjusted, and the test is carried out according to the determination part 1 of the impact performance of the GB/T1043.1-2008 plastic simple support beam: the GB/T1043.1/leA method specified by the non-instrumented impact test is carried out; molding shrinkage: the test specimens are 60mm by 2mm and, after conditioning of the test specimens, the test is carried out according to GB/T17037.4-2003 part 4 of the preparation of injection-molded test specimens of thermoplastic plastics material: the measurement of the molding shrinkage was carried out; the vertical burning test sample is 125mm multiplied by 13mm multiplied by 3mm, after the state of the sample is adjusted, the test is carried out according to the regulations of GB/T2408-2008 method B for measuring the burning performance of the plastic; thermal stability performance according to GB8965.1-2009 flame retardant protective part 1 of protective clothing: the clothes are flame-retardant.
Claims (6)
1. The halogen-free flame-retardant polyformaldehyde granule is characterized by comprising 15-20% by mass of magnesium hydroxide, and is characterized by further comprising 57-63.5% by mass of polyformaldehyde, 6-10% by mass of melamine polyphosphate, 4-7% by mass of basic sodium aluminum carbonate, 0.5-1.5% by mass of a processing aid, and the balance of a phosphorus-nitrogen flame retardant, wherein the total amount of the components is 80-85 wt% by mass of the halogen-free flame-retardant polyformaldehyde granule; the production process of the halogen-free flame-retardant polyformaldehyde granules comprises the following steps: (1) uniformly mixing magnesium hydroxide, the polyformaldehyde, the melamine polyphosphate, the phosphorus-nitrogen flame retardant, the basic aluminum sodium carbonate and the processing aid; (2) and adding the uniformly mixed materials into an extruder for extrusion, uniformly adding triethanolamine, cooling and granulating to obtain the halogen-free flame-retardant polyformaldehyde composite material.
2. The halogen-free flame-retardant polyoxymethylene pellet as claimed in claim 1, wherein the magnesium hydroxide contains 5-10 wt% of lime nitrogen.
3. The halogen-free flame-retardant polyformaldehyde pellet as claimed in claim 1, wherein the polyformaldehyde is one of homo-or co-polyformaldehyde.
4. The halogen-free flame-retardant polyoxymethylene pellet as claimed in claim 1, wherein said phosphorus-nitrogen flame retardant is at least one or more of guanidine sulfamate, diammonium hydrogen phosphate, hexaphenoxycyclotriphosphazene.
5. The halogen-free flame-retardant polyformaldehyde pellet as claimed in claim 1, wherein the triethanolamine in step (2) is added at stage 3 of the machine barrel, wherein the adding amount of the triethanolamine is 0.05-0.1 wt% of the halogen-free flame-retardant polyformaldehyde pellet.
6. The halogen-free flame-retardant polyformaldehyde pellets as claimed in claim 1, wherein the mixing in step (2) is material mixing by a high-speed mixer set, the temperature is 50 ℃, the stirring is carried out at 300rpm for 30-40 min, and the extrusion temperature is 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃ and the head temperature is 180 ℃ respectively.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1100067A (en) * | 1993-09-08 | 1995-03-15 | 屠志康 | Precipitated calcium carbonate preparation using waste from dicyandiamide plant |
| CN101851351A (en) * | 2010-06-29 | 2010-10-06 | 四川大学 | Inorganic hydroxide composite flame retardant and high-performance halogen-free flame-retardant polyformaldehyde material using same for antiflaming |
| CN102993625A (en) * | 2012-11-19 | 2013-03-27 | 开滦能源化工股份有限公司 | Halogen-free flame-retardant formaldehyde composite material with high CTI (comparative tracking index) and preparation method thereof |
| CN107619588A (en) * | 2016-07-15 | 2018-01-23 | 江阴市志远汽车饰件有限公司 | A kind of halogen-free flameproof automotive upholstery and preparation method thereof |
| CN109776861A (en) * | 2019-02-14 | 2019-05-21 | 青岛科技大学 | It is a kind of using glycol-modified melamine resin as the expansion type flame retardant of carbon forming agent |
-
2022
- 2022-05-06 CN CN202210484785.9A patent/CN114773776A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1100067A (en) * | 1993-09-08 | 1995-03-15 | 屠志康 | Precipitated calcium carbonate preparation using waste from dicyandiamide plant |
| CN101851351A (en) * | 2010-06-29 | 2010-10-06 | 四川大学 | Inorganic hydroxide composite flame retardant and high-performance halogen-free flame-retardant polyformaldehyde material using same for antiflaming |
| CN102993625A (en) * | 2012-11-19 | 2013-03-27 | 开滦能源化工股份有限公司 | Halogen-free flame-retardant formaldehyde composite material with high CTI (comparative tracking index) and preparation method thereof |
| CN107619588A (en) * | 2016-07-15 | 2018-01-23 | 江阴市志远汽车饰件有限公司 | A kind of halogen-free flameproof automotive upholstery and preparation method thereof |
| CN109776861A (en) * | 2019-02-14 | 2019-05-21 | 青岛科技大学 | It is a kind of using glycol-modified melamine resin as the expansion type flame retardant of carbon forming agent |
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