CN111718478A - Polymer flame retardant and preparation method thereof - Google Patents
Polymer flame retardant and preparation method thereof Download PDFInfo
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- CN111718478A CN111718478A CN202010575516.4A CN202010575516A CN111718478A CN 111718478 A CN111718478 A CN 111718478A CN 202010575516 A CN202010575516 A CN 202010575516A CN 111718478 A CN111718478 A CN 111718478A
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- chlorinated paraffin
- isocyanurate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6856—Dicarboxylic acids and dihydroxy compounds
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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
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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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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Abstract
The invention discloses an isocyanurate modified chlorinated paraffin polymer flame retardant and a preparation method thereof, the preparation method of the flame retardant comprises the steps of firstly preparing chlorinated paraffin containing carboxyl by reacting the chlorinated paraffin with p-hydroxybenzoic acid, then acylating the chlorinated paraffin containing carboxyl to obtain chlorinated paraffin containing acyl chloride, then carrying out esterification reaction with tris (2-hydroxyethyl) isocyanurate to obtain chlorinated paraffin containing binary hydroxyl isocyanurate modification, then carrying out acyl chlorination to obtain chlorinated paraffin containing binary acyl chloride isocyanurate modification, and finally esterifying to obtain the polymer flame retardant.
Description
Technical Field
The invention relates to an isocyanurate modified chlorinated paraffin polymer flame retardant and a preparation method thereof, belonging to the field of plastic rubber flame retardants.
Background
With the development of national economy and the improvement of the living standard of people, polymer materials such as synthetic fibers, plastics, rubbers and the like are more and more widely applied to various fields such as transportation, building materials, electronic appliances, daily furniture, interior decoration and the like. However, these polymer materials are generally flammable and easily cause fire accidents, and in order to solve the problems of flame resistance and smoke suppression of synthetic materials and to ensure the safety of the synthetic materials, the most effective method is to add a flame retardant. The halogen flame retardant has less addition amount, low cost and good compatibility with synthetic materials, and does not change the original machining performance of the flame retardant product, so the halogen flame retardant is the organic flame retardant with the largest output and use amount at present. However, the halogen-based flame retardants are limited because of problems such as decomposition to generate hydrogen halide during combustion. With the increasing awareness of flame-retardant fire prevention worldwide, the development of highly effective halogen flame retardants to reduce the amount of hydrogen halide released during combustion and to reduce the influence on the machinability of materials is an important research direction.
The chlorinated paraffin is a traditional polyvinyl chloride auxiliary additive and has the characteristics of low volatility, flame retardance, good electrical insulation, low price and the like. But the flame retardant effect is general, and the flame retardant effect needs to be improved by compounding other flame retardants when in use, so that the wide application of the flame retardant is hindered. In addition, over time, chlorinated paraffins tend to migrate out of the polymer network, reducing the durability of the flame retardant.
Disclosure of Invention
Aiming at the defects of chlorinated paraffin in the prior art, the invention aims to provide an isocyanurate modified chlorinated paraffin flame retardant with high flame retardant efficiency. The physical and chemical properties are stable, the heat resistance is good, the compatibility with high polymer materials is good, the functions of plasticization and carbon formation and dripping prevention are achieved, and the defects in the prior art can be overcome.
The invention also aims to provide a method for preparing the isocyanurate modified chlorinated paraffin, which has the advantages of wide raw material source, simple operation and mild reaction conditions.
The invention provides a polymer flame retardant, which is characterized by having a structure shown in a formula (I):
wherein, in the formula (I), R1、R2Is a chlorinated paraffin chain segment.
The invention also provides a preparation method of the polymer flame retardant, which comprises the following steps:
step (1): preparation of chlorinated paraffins containing carboxyl groups
Dissolving chlorinated paraffin in butanone, adding a certain amount of p-hydroxybenzoic acid and potassium carbonate, and heating to react under the protection of nitrogen to obtain chlorinated paraffin containing carboxyl;
step (2): preparation of chlorinated paraffins containing acid chlorides
Adding the chlorinated paraffin containing carboxyl obtained in the step (1) into a reaction kettle, and dropwise adding excessive phosphorus trichloride into the reaction kettle to react to obtain chlorinated paraffin containing acyl chloride;
and (3): preparation of chlorinated paraffin modified by isocyanuric ester containing dihydroxy
Slowly dripping the chlorinated paraffin containing acyl chloride prepared in the step (2) into a mixed system of tris (2-hydroxyethyl) isocyanurate and triethylamine serving as an acid-binding agent for esterification reaction, wherein the molar ratio of the chlorinated paraffin containing acyl chloride to the tris (2-hydroxyethyl) isocyanurate is 1-1.2: 1, and reacting to obtain chlorinated paraffin containing dihydroxy isocyanurate modification;
and (4): preparation of chlorinated paraffin modified by isocyanuric acid chloride containing dibasic acid chloride
Adding the chlorinated paraffin containing the dibasic hydroxyl group obtained in the step (3) into a reaction kettle, and dropwise adding excessive phosphorus trichloride into the reaction kettle to react to obtain chlorinated paraffin containing the modification of dibasic acyl chloride isocyanurate;
and (5): preparation of polymeric flame retardants
Slowly dropwise adding the chlorinated paraffin containing the modification of the binary acyl chloride isocyanurate obtained in the step (4) into a mixed system of the chlorinated paraffin containing the modification of the binary hydroxyl isocyanurate obtained in the step (3) and triethylamine serving as an acid-binding agent for esterification reaction, wherein the molar ratio of the chlorinated paraffin containing the modification of the binary acyl chloride isocyanurate to the chlorinated paraffin containing the modification of the binary hydroxyl isocyanurate is 1:1, and reacting to obtain the polymer flame retardant.
The preparation method of the polymer flame retardant of the invention also comprises the following preferred schemes:
in the preferable scheme, the chlorinated paraffin and the p-hydroxybenzoic acid in the step (1) react at the temperature of 55-80 ℃ for 10-30 h to prepare the chlorinated paraffin containing carboxyl.
In the preferable scheme, the chlorinated paraffin containing carboxyl in the step (2) reacts with excessive phosphorus trichloride at the temperature of 50-70 ℃ for 4-6 h to prepare chlorinated paraffin containing acyl chloride.
In a preferable scheme, the esterification reaction in the step (3) is carried out under the reaction condition that chlorinated paraffin containing acyl chloride is slowly dripped into the mixed solution of the tris (2-hydroxyethyl) isocyanurate and the acid-binding agent in an ice-water bath for reaction, and the reaction is continued in the ice-water bath for 2-4 hours after the dripping is finished.
In the preferable scheme, the chlorinated paraffin containing the modification of the dihydroxy isocyanurate in the step (4) reacts with excessive phosphorus trichloride at the temperature of 50-70 ℃ for 4-6 hours to prepare the chlorinated paraffin containing the modification of the dihydroxy isocyanurate.
In the preferable scheme, the reaction condition in the step (5) is that the chlorinated paraffin containing the modification of the binary acyl chloride isocyanurate is slowly dripped into the mixed solution of the chlorinated paraffin containing the modification of the binary hydroxyl isocyanurate and the acid-binding agent in an ice-water bath for reaction, and the reaction is continued in the ice-water bath for 4 to 6 hours after the dripping is finished.
The invention has the beneficial effects that: according to the invention, the isocyanurate is used as a bridge chain to connect the traditional chlorinated paraffin to synthesize the novel polymer flame retardant for the first time, two excellent flame-retardant elements of nitrogen and chlorine are simultaneously embedded into the branched chlorinated paraffin, and the two elements generate synergistic interaction from different flame-retardant mechanisms in a synergistic manner, so that higher flame-retardant efficiency can be expressed. The whole preparation process has the advantages of easily available raw materials, low cost, simple operation, high purity of the obtained product and high yield, and meets the requirements of industrial production.
Drawings
FIG. 1 is an infrared image of a polymeric flame retardant made in example 3.
FIG. 1: 2920cm-1And 2850cm-1Respectively represents the stretching vibration absorption peak of methylene and methyl, 1470cm-1And 1370cm-1Bending vibration absorption peak of methyl group, 1745cm-1Is the stretching of C ═ O in the ester groupVibration absorption peak, 1690cm-1And 1420cm-1Is the expansion vibration absorption peak of C ═ O in isocyanurate, 1150cm-1At the stretching vibration peak of the C-N single bond, 1230cm-1And 1050cm-1Is a characteristic absorption peak of the C-O-C ether bond of 710cm-1Here is the stretching vibration peak of the C-Cl bond.
Detailed Description
The following examples are intended to further illustrate the content of the invention, but not to limit the scope of the invention.
Example 1
(1) Preparation of chlorinated paraffin 42 containing carboxyl group: dissolving 20g of chlorinated paraffin 42 in 200mL of acetone, stirring to dissolve, adding 20g of p-hydroxybenzoic acid and 30g of potassium carbonate, and reacting at 55 ℃ for 30h under the protection of nitrogen. After the reaction is finished, hydrochloric acid is used for adjusting the pH value to 3.0, then ethanol is used for extraction, and the product is dried in vacuum at 100 ℃ for 5 hours to obtain chlorinated paraffin 42 containing carboxyl.
(2) Preparation of acid chloride-containing chlorinated paraffin 42: adding 70mol of chlorinated paraffin 42 containing carboxyl into a reaction kettle, dropwise adding 85mol of phosphorus trichloride, stirring, heating to 50 ℃, reacting for 6 hours, cooling to room temperature, standing and layering to obtain chlorinated paraffin 42 containing acyl chloride.
(3) Preparation of the chlorinated paraffin 42 modified by the isocyanate containing the dihydroxy: adding 100mol of tris (2-hydroxyethyl) isocyanurate and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding dichloromethane solution containing 102mol of chlorinated paraffin 42 containing acyl chloride at 0 ℃, reacting the reactants at 0 ℃ for 2h, washing the reaction product with 4% sodium bicarbonate solution until the pH value is 7, transferring the reaction product to ethyl acetate for extraction and separation, washing the organic phase with distilled water, drying with anhydrous calcium chloride, drying for 8h, filtering under reduced pressure, and distilling the filtrate to remove the solvent to obtain the chlorinated paraffin 42 modified by the binary hydroxyl isocyanurate.
(4) Preparation of chlorinated paraffin 42 modified by containing diacid chloride isocyanurate: adding 70mol of chlorinated paraffin 42 modified by containing dibasic hydroxyl isocyanurate into a reaction kettle, dripping 85mol of phosphorus trichloride, stirring and heating to 70 ℃, reacting for 4 hours, cooling to room temperature, standing and layering to obtain chlorinated paraffin 42 modified by containing dibasic acyl chloride isocyanurate.
(5) Preparation of polymeric flame retardant: adding 100mol of chlorinated paraffin 42 modified by dibasic hydroxyl isocyanurate and a proper amount of anhydrous triethylamine as an acid-binding agent into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding dichloromethane solution containing 100mol of chlorinated paraffin 42 modified by dibasic acyl chloride isocyanurate at 0 ℃, reacting the reactants for 4 hours at 0 ℃, washing and filtering the reaction product, and drying to obtain the polymer flame retardant M1.
Example 2
(1) Preparation of chlorinated paraffin 52 containing carboxyl group: dissolving 20g of chlorinated paraffin 52 in 200mL of acetone, stirring to dissolve, adding 20g of p-hydroxybenzoic acid and 30g of potassium carbonate, and reacting at 80 ℃ for 10 hours under the protection of nitrogen. After the reaction is finished, hydrochloric acid is used for adjusting the pH value to 3.0, then ethanol is used for extraction, and the product is dried in vacuum at 100 ℃ for 5 hours to obtain chlorinated paraffin 52 containing carboxyl.
(2) Preparation of chlorinated paraffin 52 containing acid chloride: adding 70mol of carboxyl-containing chlorinated paraffin 52 into a reaction kettle, dropwise adding 85mol of phosphorus trichloride, stirring, heating to 70 ℃, reacting for 4 hours, cooling to room temperature, standing and layering to obtain the chlorinated paraffin 52 containing acyl chloride.
(3) Preparation of the chlorinated paraffin 52 modified by the isocyanuric ester containing the dibasic hydroxyl: adding 100mol of tris (2-hydroxyethyl) isocyanurate and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding dichloromethane solution containing 103mol of chlorinated paraffin 52 containing acyl chloride at 0 ℃, reacting the reactants at 0 ℃ for 4h, washing the reaction product with 4% sodium bicarbonate solution until the pH value is 7, transferring the reaction product to ethyl acetate for extraction and separation, washing the organic phase with distilled water, drying with anhydrous calcium chloride, drying for 8h, filtering under reduced pressure, and distilling the filtrate to remove the solvent to obtain the chlorinated paraffin 52 containing the binary hydroxyl isocyanurate modification.
(4) Preparation of chlorinated paraffin 52 modified by containing diacid chloride isocyanurate: adding 70mol of chlorinated paraffin 52 modified by containing dibasic hydroxyl isocyanurate into a reaction kettle, dripping 85mol of phosphorus trichloride, stirring and heating to 50 ℃, reacting for 6 hours, cooling to room temperature, standing and layering to obtain chlorinated paraffin 52 modified by containing dibasic acyl chloride isocyanurate.
(5) Preparation of polymeric flame retardant: adding 100mol of chlorinated paraffin 52 modified by dibasic hydroxyl isocyanurate and a proper amount of anhydrous triethylamine as an acid-binding agent into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding dichloromethane solution containing 100mol of chlorinated paraffin 52 modified by dibasic acyl chloride isocyanurate at 0 ℃, reacting the reactants for 6 hours at 0 ℃, washing and filtering the reaction product, and drying to obtain the polymer flame retardant M2.
Example 3
(1) Preparation of carboxyl group-containing chlorinated paraffin 70: dissolving 20g of chlorinated paraffin 52 in 200mL of acetone, stirring to dissolve, adding 20g of p-hydroxybenzoic acid and 30g of potassium carbonate, and reacting at 65 ℃ for 24h under the protection of nitrogen. After the reaction is finished, hydrochloric acid is used for adjusting the pH value to 3.0, then ethanol is used for extraction, and the product is dried in vacuum at 100 ℃ for 5 hours to obtain chlorinated paraffin 70 containing carboxyl.
(2) Preparation of acid chloride-containing chlorinated paraffin 70: adding 70mol of carboxyl-containing chlorinated paraffin 70 into a reaction kettle, dropwise adding 85mol of phosphorus trichloride, stirring, heating to 60 ℃, reacting for 5 hours, cooling to room temperature, standing and layering to obtain the chlorinated paraffin 70 containing acyl chloride.
(3) Preparation of the dihydric hydroxyl isocyanurate-containing modified chlorinated paraffin 70: adding 100mol of tris (2-hydroxyethyl) isocyanurate and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding a dichloromethane solution containing 101mol of chlorinated paraffin 70 containing acyl chloride at 0 ℃, reacting the reactants at 0 ℃ for 3h, washing the reaction product with 4% sodium bicarbonate solution until the pH value is 7, transferring the reaction product to ethyl acetate for extraction and separation, washing the organic phase with distilled water, drying the organic phase with anhydrous calcium chloride, drying the organic phase for 8h, filtering the organic phase under reduced pressure, and distilling the filtrate to remove the solvent to obtain the chlorinated paraffin 70 containing the binary hydroxyl isocyanurate modification.
(4) Preparation of chlorinated paraffin 70 modified by containing dibasic acyl chloride isocyanurate: adding 70mol of chlorinated paraffin 70 modified by containing dibasic hydroxyl isocyanurate into a reaction kettle, dripping 85mol of phosphorus trichloride, stirring and heating to 60 ℃, reacting for 5 hours, cooling to room temperature, standing and layering to obtain chlorinated paraffin 70 modified by containing dibasic acyl chloride isocyanurate.
(5) Preparation of polymeric flame retardant: adding 100mol of chlorinated paraffin 70 modified by dibasic hydroxyl isocyanurate and a proper amount of anhydrous triethylamine as an acid-binding agent into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding dichloromethane solution containing 100mol of chlorinated paraffin 70 modified by dibasic acyl chloride isocyanurate at 0 ℃, reacting the reactants for 5 hours at 0 ℃, washing and filtering the reaction product, and drying to obtain the polymer flame retardant M3.
The inventor applies the prepared isocyanurate modified chlorinated paraffin polymer flame retardant to polyvinyl chloride. The flame retardant property of the product in polyvinyl chloride is measured by referring to GB/T2406-2008 'Plastic burning property test method-oxygen index method'. Selecting different flame retardants, dioctyl phthalate (DOP) and synergistic flame retardant antimony trioxide (Sb)2O3) The sample is uniformly mixed with polyvinyl chloride (PVC) according to the proportion in the formula, extruded by an extruder, made into a sample strip with the length of 15cm and the diameter of 3mm, and tested for physical and flame retardant properties, and the test results are shown in Table 1. Formula (by mass): 100 parts of PVC, 50 parts of plasticizer (DOP), and antimony trioxide (Sb)2O3)5 parts of flame retardant and 40 parts of flame retardant.
Table 1 performance data of the isocyanurate-modified chlorinated paraffin polymer flame retardants synthesized in examples 1-3:
in conclusion, the chlorinated paraffin molecules are connected into a novel polymer flame retardant through the isocyanurate, two excellent flame retardant elements, namely nitrogen and chlorine, are embedded into the chlorinated paraffin molecules, the flame retardant effect of the nitrogen element is increased on the basis of high-efficiency chlorine flame retardance, and the two elements generate synergistic interaction from different flame retardant mechanisms in a synergistic manner, so that higher flame retardant efficiency can be shown.
Claims (7)
1. A polymeric flame retardant characterized by having the structure of formula (I):
wherein, in the formula (I), R1、R2Is a chlorinated paraffin chain segment.
2. A preparation method of a polymer flame retardant is characterized by comprising the following steps:
step (1): preparation of chlorinated paraffins containing carboxyl groups
Dissolving chlorinated paraffin in butanone, adding a certain amount of p-hydroxybenzoic acid and potassium carbonate, and heating to react under the protection of nitrogen to obtain chlorinated paraffin containing carboxyl;
step (2): preparation of chlorinated paraffins containing acid chlorides
Adding the chlorinated paraffin containing carboxyl obtained in the step (1) into a reaction kettle, and dropwise adding excessive phosphorus trichloride into the reaction kettle to react to obtain chlorinated paraffin containing acyl chloride;
and (3): preparation of chlorinated paraffin modified by isocyanuric ester containing dihydroxy
Slowly dripping the chlorinated paraffin containing acyl chloride prepared in the step (2) into a mixed system of tris (2-hydroxyethyl) isocyanurate and triethylamine serving as an acid-binding agent for esterification reaction, wherein the molar ratio of the chlorinated paraffin containing acyl chloride to the tris (2-hydroxyethyl) isocyanurate is 1-1.2: 1, and reacting to obtain chlorinated paraffin containing dihydroxy isocyanurate modification;
and (4): preparation of chlorinated paraffin modified by isocyanuric acid chloride containing dibasic acid chloride
Adding the chlorinated paraffin containing the dibasic hydroxyl group obtained in the step (3) into a reaction kettle, and dropwise adding excessive phosphorus trichloride into the reaction kettle to react to obtain chlorinated paraffin containing the modification of dibasic acyl chloride isocyanurate;
and (5): preparation of polymeric flame retardants
Slowly dropwise adding the chlorinated paraffin containing the modification of the binary acyl chloride isocyanurate obtained in the step (4) into a mixed system of the chlorinated paraffin containing the modification of the binary hydroxyl isocyanurate obtained in the step (3) and triethylamine serving as an acid-binding agent for esterification reaction, wherein the molar ratio of the chlorinated paraffin containing the modification of the binary acyl chloride isocyanurate to the chlorinated paraffin containing the modification of the binary hydroxyl isocyanurate is 1:1, and reacting to obtain the polymer flame retardant.
3. The method according to claim 2, wherein the chlorinated paraffin containing carboxyl group is prepared by reacting the chlorinated paraffin with p-hydroxybenzoic acid in the step (1) at a temperature of 55-80 ℃ for 10-30 hours.
4. The preparation method of claim 2, wherein the chlorinated paraffin containing carboxyl in the step (2) reacts with excess phosphorus trichloride at a temperature of 50-70 ℃ for 4-6 h to obtain chlorinated paraffin containing acyl chloride.
5. The preparation method of claim 2, wherein the esterification reaction in the step (3) is carried out under the reaction conditions that chlorinated paraffin containing acyl chloride is slowly added dropwise into the mixed solution of tris (2-hydroxyethyl) isocyanurate and the acid-binding agent in an ice-water bath for reaction, and after the dropwise addition is completed, the reaction is continued in the ice-water bath for 2-4 hours.
6. The preparation method of claim 2, wherein the chlorinated paraffin modified by dihydroxy isocyanurate in step (4) is reacted with excess phosphorus trichloride at 50-70 ℃ for 4-6 h to obtain chlorinated paraffin modified by dihydroxy isocyanurate.
7. The preparation method of claim 2, wherein the reaction conditions in the step (5) are that firstly, the chlorinated paraffin modified by the binary acyl chloride containing isocyanurate is slowly dripped into the mixed solution of the chlorinated paraffin modified by the binary hydroxyl containing isocyanurate and the acid binding agent in an ice-water bath for reaction, and after the dripping is completed, the reaction is continued in the ice-water bath for 4-6 hours.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112760013A (en) * | 2021-01-20 | 2021-05-07 | 邓万菁 | Flame-retardant fireproof coiled material and preparation method thereof |
| CN112812679A (en) * | 2021-01-20 | 2021-05-18 | 张雪飞 | Polyurethane flame-retardant floor coating |
| CN112876976A (en) * | 2021-01-20 | 2021-06-01 | 张雪飞 | Polyurethane flame-retardant floor coating and preparation method thereof |
-
2020
- 2020-06-22 CN CN202010575516.4A patent/CN111718478A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112760013A (en) * | 2021-01-20 | 2021-05-07 | 邓万菁 | Flame-retardant fireproof coiled material and preparation method thereof |
| CN112812679A (en) * | 2021-01-20 | 2021-05-18 | 张雪飞 | Polyurethane flame-retardant floor coating |
| CN112876976A (en) * | 2021-01-20 | 2021-06-01 | 张雪飞 | Polyurethane flame-retardant floor coating and preparation method thereof |
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