CN112876976A - Polyurethane flame-retardant floor coating and preparation method thereof - Google Patents
Polyurethane flame-retardant floor coating and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
- C10G73/38—Chemical modification of petroleum
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- 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
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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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 a polyurethane flame-retardant floor coating, which comprises a chlorinated paraffin modified diamine vulcanizing agent, wherein the preparation method of the diamine vulcanizing agent comprises the steps of preparing chlorinated paraffin containing carboxyl by reacting the chlorinated paraffin with p-hydroxybenzoic acid, preparing modified chlorinated paraffin diacid by performing esterification reaction on the chlorinated paraffin containing carboxyl and 2, 5-dihydroxy terephthalic acid, and then reacting the modified chlorinated paraffin diacid with 1, 3-propane diamine to obtain the chlorinated paraffin modified diamine vulcanizing agent.
Description
Technical Field
The invention relates to a polyurethane flame-retardant floor coating and a preparation method thereof, belonging to the field of chemical flame-retardant coatings.
Background
The polyurethane floor coating is a ground decoration material which is synthesized by polyurethane raw materials, added with pigment, auxiliary agent and curing agent and prepared. The polyurethane floor coating is made into a floor which can meet certain specific use requirements by combining with a specific construction technology. The polyurethane terrace is convenient to construct, can replace an epoxy terrace, has higher wear resistance and flexibility, and different construction environments can emphasize different index requirements, such as a high-grade conference or an entertainment center emphasizes comfort requirements, industrial and mining enterprises emphasize corrosion resistance and wear resistance requirements, a food industry emphasizes high and low temperature resistance, and a logistics industry requires rapid use.
Polyurethane floor coatings are soft and gentle and provide sufficient comfort for the movement of people or vehicles in the area. The elastic floor material solution not only reduces horizontal noise transmission, but also resists scratches through self-deformation and recovery. Generally speaking, the polyether structure on the polyurethane molecular chain determines that the polyurethane product is flammable, relatively strict requirements are made on the combustion performance of the floor coating on certain occasions with higher fireproof requirements, and the mode of adding the auxiliary flame retardant can partially solve the contradiction.
The chlorinated paraffin is a chlorinated derivative of paraffin, has the advantages of low volatility, flame retardance, good barrier property, low price and the like, can be used as additives such as a plasticizer, a flame retardant and the like, and is already used in a large amount in a flame retardant material, but the addition amount of an additive type flame retardant is relatively large, and the flame retardant property is general. As the service time is prolonged, the additive flame retardant is easy to migrate out of the polymer network, causes pollution to the environment, and reduces the mechanical properties of the material and the durability of flame retardance.
Disclosure of Invention
Aiming at the defects of chlorinated paraffin in the application of polyurethane flame-retardant floor materials in the prior art, the invention aims to provide a chlorinated paraffin modified diamine vulcanizing agent for polyurethane.
The invention also aims to provide a method for preparing the chlorinated paraffin modified diamine vulcanizing agent, which has the advantages of wide raw material source, simple operation and mild reaction conditions.
The polyurethane flame-retardant floor coating is characterized by consisting of polyether polyol, aluminum hydroxide, chlorinated paraffin modified diamine vulcanizing agent and curing agent; the chlorinated paraffin modified diamine vulcanizing agent has a structure shown in a formula (I):
wherein R is1、R2Is a chlorinated paraffin chain segment.
The invention also provides a preparation method of the chlorinated paraffin modified diamine vulcanizing agent, 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
Carrying out phosphorus trichloride acylation on the chlorinated paraffin containing carboxyl obtained in the step (1) to obtain chlorinated paraffin containing acyl chloride;
and (3): preparation of modified chlorinated Paraffin dibasic acid
Slowly dripping the chlorinated paraffin containing acyl chloride prepared in the step (2) into a mixed system of 2, 5-dihydroxy terephthalic acid and acid-binding agent triethylamine under the protection of nitrogen to perform esterification reaction to obtain modified chlorinated paraffin dibasic acid;
and (4): preparation of modified chlorinated Paraffin Dichloride
Carrying out phosphorus trichloride acylation on the modified chlorinated paraffin diacid obtained in the step (3) to obtain modified chlorinated paraffin diacid chloride;
and (5): preparation of chlorinated Paraffin modified diamines
Slowly and dropwisely adding the modified chlorinated paraffin diacid chloride prepared in the step (4) into a mixed system of 1, 3-propane diamine and acid-binding agent triethylamine under the protection of nitrogen to perform amidation reaction to obtain chlorinated paraffin modified diamine.
The preparation method of the chlorinated paraffin modified diamine vulcanizing agent also comprises the following preferred scheme:
preferably, the chlorinated paraffin containing carboxyl is prepared by reacting the chlorinated paraffin with p-hydroxybenzoic acid in the step (1) at the temperature of 55-80 ℃ for 10-30 h.
Preferably, 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.
More preferably, the mole ratio of the chlorinated paraffin containing acyl chloride and the 2, 5-dihydroxy terephthalic acid in the step (3) is 2-2.2: 1.
Preferably, 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 2, 5-dihydroxy terephthalic acid and the acid binding agent at the temperature of 15-25 ℃ for reaction, and the reaction is continued for 3-5 hours after the dripping is finished.
Preferably, the modified chlorinated paraffin diacid reacts with excessive phosphorus trichloride for 4-6 hours at the temperature of 50-70 ℃ in the step (4) to prepare the modified chlorinated paraffin diacid chloride.
Further preferably, the molar ratio of the modified chlorinated paraffin diacid chloride reacted with the 1, 3-propane diamine in the step (5) is 1-1.1: 2.
Preferably, in the step (5), the reaction condition is that the modified chlorinated paraffin diacid chloride is slowly dripped into the mixed solution of the 1, 3-propane diamine and the acid-binding agent in an ice water bath for reaction, after the dripping is finished, the temperature is raised to 20-40 ℃, and the reaction is continued for 1-2 hours.
The invention has the beneficial effects that: according to the invention, the traditional chlorinated paraffin molecule is modified through a chemical bond for the first time to form a novel diamine vulcanizing agent with a rigid benzene ring in a molecule main chain, and the chlorinated paraffin molecule chain is introduced into the floor coating through later-stage curing of the polyurethane flame-retardant floor coating, so that the material is endowed with excellent flame-retardant performance, the chlorinated paraffin molecule cannot migrate outside the material to cause pollution to the environment, the durability of the flame-retardant effect of the material is ensured, and the flame-retardant polyurethane flame-retardant coating is particularly suitable for places with higher requirements on environmental protection and flame retardance, such as meeting rooms, child playgrounds, gas stations and the like. 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 the chlorinated paraffin-modified diamine curative prepared in example 1.
FIG. 1: 3300cm-1Is the absorption peak of N-H stretching vibration, 3030cm-12910cm as the C-H stretching vibration absorption peak on the benzene ring-1And 2850cm-1Is the absorption peak of stretching vibration of methyl and methylene, 1470cm-1And 1370cm-11750cm as bending vibration absorption peak of methyl-1Is the stretching vibration absorption peak of C ═ O in the ester group, 1660cm-1Absorption peak of carbonyl group in amide, 1520cm-1Is a bending vibration absorption peak of N-H and a stretching vibration absorption peak of C-N in amide, and is 1490cm-Is the characteristic absorption peak of benzene ring, 1225cm-1And 1055cm-1Is a characteristic absorption peak of the C-O-C ether bond of 510cm-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: 20g of chlorinated paraffin 42 is dissolved in 210mL of acetone, stirred and dissolved, and then 20g of p-hydroxybenzoic acid and 28g of potassium carbonate are added to react for 30h at 55 ℃ 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 70 ℃, reacting for 4 hours, cooling to room temperature, standing and layering to obtain chlorinated paraffin 42 containing acyl chloride.
(3) Preparation of chlorinated paraffin 42 modified dibasic acid: adding 50mol of 2, 5-dihydroxyterephthalic acid 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 42 containing acyl chloride at 15 ℃, continuing to react for 5 hours after dropwise adding, and washing and drying a reaction product to obtain the chlorinated paraffin 42 modified dibasic acid.
(4) Preparation of chlorinated paraffin 42 modified diacid chloride: adding 70mol of chlorinated paraffin 42 modified dibasic acid into a reaction kettle, dropwise adding 100mol of phosphorus trichloride, stirring and heating to 50 ℃, reacting for 6 hours, cooling to room temperature, standing and layering to obtain chlorinated paraffin 42 modified diacid chloride.
(5) Preparation of chlorinated paraffin 42 modified diamine: adding 100mol of anhydrous dichloromethane, 100mol of 1, 3-propane diamine and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding 50mol of dichloromethane solution containing chlorinated paraffin 42 modified diacid chloride at 0 ℃, heating to 20 ℃ after dropwise adding, continuing to react for 2h, washing and drying a reaction product to obtain chlorinated paraffin 42 modified diamine vulcanizing agent G1.
Example 2
(1) Preparation of chlorinated paraffin 52 containing carboxyl group: 20g of chlorinated paraffin 52 is dissolved in 220mL of acetone, stirred and dissolved, and then 20g of p-hydroxybenzoic acid and 29g of potassium carbonate are added to react for 10 hours at 80 ℃ 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 50 ℃, reacting for 6 hours, cooling to room temperature, standing and layering to obtain the chlorinated paraffin 52 containing acyl chloride.
(3) Preparation of chlorinated paraffin 52 modified dibasic acid: adding 50mol of 2, 5-dihydroxyterephthalic acid 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 103mol of chlorinated paraffin 52 containing acyl chloride at 25 ℃, continuing to react for 3 hours after dropwise adding, and washing and drying a reaction product to obtain the chlorinated paraffin 52 modified dibasic acid.
(4) Preparation of chlorinated paraffin 52 modified diacid chloride: adding 70mol of chlorinated paraffin 52 modified dibasic acid into a reaction kettle, dropwise adding 100mol of phosphorus trichloride, stirring and heating to 70 ℃, reacting for 4 hours, cooling to room temperature, standing and layering to obtain chlorinated paraffin 52 modified diacid chloride.
(5) Preparation of chlorinated paraffin 52 modified diamine: adding 100mol of anhydrous dichloromethane, 100mol of 1, 3-propane diamine and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding 50mol of dichloromethane solution containing chlorinated paraffin 52 modified diacid chloride at 0 ℃, heating to 40 ℃ after dropwise adding, continuing to react for 1h, washing and drying a reaction product to obtain chlorinated paraffin 52 modified diamine vulcanizing agent G2.
Example 3
(1) Preparation of carboxyl group-containing chlorinated paraffin 70: dissolving 20g of chlorinated paraffin 70 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 chlorinated paraffin 70 modified dibasic acid: adding 50mol of 2, 5-dihydroxyterephthalic acid 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 102mol of chlorinated paraffin 70 containing acyl chloride at 20 ℃, continuing to react for 4 hours after dropwise adding, and washing and drying a reaction product to obtain the chlorinated paraffin 70 modified dibasic acid.
(4) Preparation of chlorinated paraffin 70 modified diacid chloride: adding 70mol of chlorinated paraffin 70 modified dibasic acid into a reaction kettle, dropwise adding 100mol of phosphorus trichloride, stirring and heating to 70 ℃, reacting for 4 hours, cooling to room temperature, standing and layering to obtain chlorinated paraffin 70 modified diacid chloride.
(5) Preparation of chlorinated paraffin 70 modified diamine: adding 100mol of anhydrous dichloromethane, 100mol of 1, 3-propane diamine and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding 50mol of dichloromethane solution containing chlorinated paraffin 70 modified diacid chloride at 0 ℃, heating to 35 ℃ after dropwise adding, continuing to react for 1h, washing and drying a reaction product to obtain chlorinated paraffin 70 modified diamine vulcanizing agent G3.
Preparation and test of polyurethane flame-retardant floor coating
Adding 70 parts by weight of toluene diisocyanate, 10 parts by weight of polyether N-330 and 23 parts by weight of polyether N-220 into a sealed reaction kettle at 85 ℃, stirring and reacting for 5 hours, cooling to 40 ℃, adding 0.8 part by weight of p-toluene sulfonyl isocyanate, and stirring for 50 minutes to obtain the polyurethane curing agent.
Adding polyether polyol N330, p-phenylenediamine, chlorinated paraffin modified diamine vulcanizing agent, chlorinated paraffin 52 and aluminum hydroxide into a reaction kettle according to the weight parts of the raw materials in the table 1, heating to 100 ℃, uniformly stirring, carrying out vacuum dehydration for 3 hours, and reducing the temperature to room temperature to obtain the combined polyol. And then, obtaining the polyurethane flame-retardant floor coating by the polyurethane curing agent and the combined polyol according to the reaction molar ratio of 1:1, and testing the surface drying time, the actual drying time, the peeling strength, the tensile strength, the elongation at break, the friction coefficient, the wear resistance and the flame retardance of the floor coating according to the national standard, wherein the test results are shown in table 2.
TABLE 1 combination polyol formulation
Table 2 polyurethane flame retardant floor coatings test results
Note: v-0 and V-1 are fire test ratings of class V, where V-0 is better than V-1 and NR indicates failure of the test.
In conclusion, the traditional chlorinated paraffin molecule is modified by chemical bonds to form a novel diamine vulcanizing agent with a rigid benzene ring in a molecular main chain, so that the formed polyurethane flame-retardant floor coating has excellent mechanical property and flame retardant property, the chlorinated paraffin molecule cannot migrate outside the material to pollute the environment, the durability of the flame retardant effect of the material is ensured, and the polyurethane flame-retardant floor coating is particularly suitable for places with higher requirements on environmental protection and flame retardance, such as meeting rooms, child amusement places, gas stations and the like.
Claims (9)
1. The polyurethane flame-retardant floor coating is characterized by consisting of polyether polyol, aluminum hydroxide, chlorinated paraffin modified diamine vulcanizing agent and curing agent; the chlorinated paraffin modified diamine vulcanizing agent has a structure shown in a formula (I):
wherein R is1、R2Is a chlorinated paraffin chain segment.
2. The preparation method of the chlorinated paraffin modified diamine vulcanizing agent 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
Carrying out phosphorus trichloride acylation on the chlorinated paraffin containing carboxyl obtained in the step (1) to obtain chlorinated paraffin containing acyl chloride;
and (3): preparation of modified chlorinated Paraffin dibasic acid
Slowly dripping the chlorinated paraffin containing acyl chloride prepared in the step (2) into a mixed system of 2, 5-dihydroxy terephthalic acid and acid-binding agent triethylamine under the protection of nitrogen to perform esterification reaction to obtain modified chlorinated paraffin dibasic acid;
and (4): preparation of modified chlorinated Paraffin Dichloride
Carrying out phosphorus trichloride acylation on the modified chlorinated paraffin diacid obtained in the step (3) to obtain modified chlorinated paraffin diacid chloride;
and (5): preparation of chlorinated Paraffin modified diamines
Slowly and dropwisely adding the modified chlorinated paraffin diacid chloride prepared in the step (4) into a mixed system of 1, 3-propane diamine and acid-binding agent triethylamine under the protection of nitrogen to perform amidation reaction to obtain chlorinated paraffin modified diamine.
3. The method according to claim 2, wherein the chlorinated paraffin containing a 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 according to claim 2, wherein the chlorinated paraffin containing carboxyl groups in the step (2) is reacted with excess phosphorus trichloride at a temperature of 50-70 ℃ for 4-6 h to prepare chlorinated paraffin containing acyl chloride.
5. The method according to claim 2, wherein the mole ratio of the acid chloride-containing chlorinated paraffin to the 2, 5-dihydroxyterephthalic acid in the step (3) is 2 to 2.2: 1.
6. The preparation method according to claim 2, wherein the esterification reaction in the step (3) is carried out under the reaction condition that chlorinated paraffin containing acyl chloride is slowly added dropwise into the mixed solution of 2, 5-dihydroxyterephthalic acid and the acid-binding agent at the temperature of 15-25 ℃ for reaction, and the reaction is continued for 3-5 hours after the dropwise addition is completed.
7. The method according to claim 2, wherein the modified chlorinated paraffin diacid in the step (4) reacts with excess phosphorus trichloride at a temperature of 50-70 ℃ for 4-6 h to obtain the modified chlorinated paraffin diacid chloride.
8. The method according to claim 2, wherein the modified chlorinated paraffin diacid chloride is reacted with 1, 3-propane diamine in a molar ratio of 1 to 1.1:2 in step (5).
9. The preparation method of claim 2, wherein the reaction conditions in the step (5) are that the modified chlorinated paraffin diacid chloride is slowly dripped into the mixed solution of the 1, 3-propane diamine and the acid-binding agent in an ice-water bath for reaction, after the dripping is completed, the temperature is raised to 20-40 ℃, and the reaction is continued for 1-2 hours.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134442A (en) * | 2010-01-26 | 2011-07-27 | 北京建筑材料科学研究总院有限公司 | Method for preparing single-component flame retardant polyurethane floor coating |
| CN105273609A (en) * | 2015-11-19 | 2016-01-27 | 成都市嘉洲新型防水材料有限公司 | High-strength environment-friendly polyurethane flame-retardant and waterproof paint and preparation method thereof |
| CN111718478A (en) * | 2020-06-22 | 2020-09-29 | 欧阳杰 | Polymer flame retardant and preparation method thereof |
-
2021
- 2021-01-20 CN CN202110076061.6A patent/CN112876976A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134442A (en) * | 2010-01-26 | 2011-07-27 | 北京建筑材料科学研究总院有限公司 | Method for preparing single-component flame retardant polyurethane floor coating |
| CN105273609A (en) * | 2015-11-19 | 2016-01-27 | 成都市嘉洲新型防水材料有限公司 | High-strength environment-friendly polyurethane flame-retardant and waterproof paint and preparation method thereof |
| CN111718478A (en) * | 2020-06-22 | 2020-09-29 | 欧阳杰 | Polymer flame retardant and preparation method thereof |
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