CN112877098A - Polymer flame retardant and preparation method thereof - Google Patents
Polymer flame retardant and preparation method thereof Download PDFInfo
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- CN112877098A CN112877098A CN202110059162.2A CN202110059162A CN112877098A CN 112877098 A CN112877098 A CN 112877098A CN 202110059162 A CN202110059162 A CN 202110059162A CN 112877098 A CN112877098 A CN 112877098A
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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
- 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 a polymer flame retardant, which is prepared by the steps of firstly preparing chlorinated paraffin containing carboxyl by the reaction of chlorinated paraffin and p-hydroxybenzoic acid, then acylating the chlorinated paraffin containing carboxyl to obtain chlorinated paraffin containing acyl chloride, then respectively obtaining chlorinated paraffin modified by isocyanurate containing monohydric hydroxyl and dihydric hydroxyl by esterification with tris (2-hydroxyethyl) isocyanurate, then reacting the product containing monohydric hydroxyl with trimellitic anhydride to obtain dibasic acid, and carrying out polymerization reaction on the dibasic acid and the chlorinated paraffin modified by the isocyanurate containing dihydric hydroxyl to prepare the polymer flame retardant.
Description
Technical Field
The invention relates to a 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.
According to the invention, two excellent flame-retardant elements, namely nitrogen and chlorine, are embedded into the isocyanurate-modified chlorinated paraffin polymer flame retardant 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 expressed. The aromatic heterocyclic structure in the molecule has the multi-directionality of an electronic structure and the fusion property of a polyester structure, so that the compatibility of the polymer flame retardant and high polymer materials such as polyvinyl chloride and the like can be improved; the polymer flame retardant has high efficiency and wide application, and can generate better economic benefit.
Disclosure of Invention
Aiming at the defects of chlorinated paraffin in the prior art, the invention aims to provide an isocyanurate modified chlorinated paraffin polymer flame retardant with high flame retardant efficiency. The product has stable physical and chemical properties, good heat resistance and good compatibility with high polymer materials, has the function of preventing charing and dropping, and can overcome the defects in the prior art.
The invention also aims to provide a method for preparing the isocyanurate modified chlorinated paraffin polymer flame retardant, which has the advantages of wide raw material source, simple operation and mild reaction conditions.
The invention provides an isocyanurate modified chlorinated paraffin polymer flame retardant, which has a structure shown in a formula (I):
in the formula (I), R1、R2、R3Is 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 acetone, 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 hydroxyl-containing isocyanurate modified chlorinated Paraffin
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 or 2-2.2: 1, and respectively obtaining chlorinated paraffin containing binary or monobasic hydroxyl;
and (4): preparation of carboxyl-containing isocyanurate-modified chlorinated Paraffin
Adding the chlorinated paraffin containing the monohydric hydroxyl and trimellitic anhydride obtained in the step (3) into a reaction kettle, and reacting to obtain chlorinated paraffin containing carboxyl isocyanurate modification;
and (5): preparation of polymeric flame retardants
And (3) adding the chlorinated paraffin modified by the isocyanurates containing carboxyl obtained in the step (4), the chlorinated paraffin modified by the isocyanurates containing dihydric hydroxyl obtained in the step (3), adding a proper amount of p-toluenesulfonic acid and a proper amount of toluene or cyclohexane as a water-carrying agent into a reaction kettle, and heating to react to obtain the polymer flame retardant.
The preparation method of the polymer flame retardant comprises the following preferred schemes:
preferably, the chlorinated paraffin and the p-hydroxybenzoic acid react at the temperature of 55-80 ℃ for 10-30 h to prepare the chlorinated paraffin containing carboxyl.
Preferably, the chlorinated paraffin containing carboxyl reacts with excessive phosphorus trichloride at the temperature of 50-70 ℃ for 4-6 h to prepare chlorinated paraffin containing acyl chloride.
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 tris (2-hydroxyethyl) isocyanurate and the acid-binding agent in an ice-water bath for reaction, and after the dripping is finished, the reaction is continuously carried out in the ice-water bath for 2-4 hours.
Preferably, in the step (4), the chlorinated paraffin containing the monohydroxy group and trimellitic anhydride react for 3-7 h at the temperature of 60-80 ℃ to obtain the chlorinated paraffin containing the carboxyl group and the isocyanurate modification.
Further preferably, the reaction condition in the step (5) is that the reaction is carried out for 5-10 hours at the temperature of 120-190 ℃.
The invention has the beneficial effects that: according to the invention, the traditional chlorinated paraffin molecule is introduced into an isocyanurate molecular chain through a chemical bond for the first time to form a novel dihydric alcohol and a dibasic acid, and then the novel dihydric alcohol and the dibasic acid are polymerized into a polymer flame retardant through an esterification reaction. 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 chart of the polymer flame retardant obtained in example 3.
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 210mL of acetone, stirring to dissolve, adding 20g of p-hydroxybenzoic acid and 28g 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 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 4 hours, cooling to room temperature, standing and layering to obtain chlorinated paraffin 42 containing acyl chloride.
3) Preparation of isocyanurate modified chlorinated paraffin 42 monohydric alcohol: 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 201mol of chlorinated paraffin 42 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 42 modified by the monohydroxy isocyanurate.
4) Preparation of isocyanurate modified chlorinated paraffin 42 diol: 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 42 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 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 42 containing the binary hydroxyl isocyanurate modification.
5) Preparation of chlorinated paraffin modified by isocyanuric ester containing carboxyl: adding 100mol of carbon tetrachloride, 70mol of monohydroxy isocyanurate-containing modified chlorinated paraffin 42 and 70mol of trimellitic anhydride into a reaction kettle, introducing nitrogen into the reaction kettle, stirring and heating to 70 ℃, reacting for 4h, cooling, extracting and separating with ethyl acetate, drying an organic phase with anhydrous calcium chloride, drying for 8h, filtering under reduced pressure, and distilling the filtrate to remove the solvent to obtain the isocyanurate-modified chlorinated paraffin 42 dibasic acid.
6) Preparation of polymeric flame retardant: 100mol of isocyanuric ester modified chlorinated paraffin 42 diacid, 100mol of isocyanuric ester modified chlorinated paraffin 42 containing dihydroxy and a proper amount of p-toluenesulfonic acid are added into a reaction kettle, nitrogen is introduced into the reaction kettle, the reaction is carried out for 3 hours at 190 ℃ until no water is generated, and the reaction is stopped. Cooling, filtering and rotary steaming to obtain a crude product. Vacuum distilling to obtain Z1.
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 24h at 65 ℃ 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 isocyanurate-modified chlorinated paraffin 52 monohydric alcohol: 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 202mol of chlorinated paraffin 52 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 52 containing monohydroxy isocyanurate modification.
4) Preparation of isocyanurate modified chlorinated paraffin 52 dihydric alcohol: 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 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 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.
5) Preparation of chlorinated paraffin modified by isocyanuric ester containing carboxyl: adding 100mol of carbon tetrachloride, 70mol of monohydroxy isocyanurate-containing modified chlorinated paraffin 52 and 70mol of trimellitic anhydride into a reaction kettle, introducing nitrogen into the reaction kettle, stirring and heating to 70 ℃, reacting for 3h, cooling, extracting and separating with ethyl acetate, drying an organic phase with anhydrous calcium chloride, drying for 8h, filtering under reduced pressure, and distilling the filtrate to remove the solvent to obtain the isocyanurate-modified chlorinated paraffin 52 dibasic acid.
6) Preparation of polymeric flame retardant: 100mol of isocyanuric ester modified chlorinated paraffin 52 diacid, 100mol of isocyanuric ester modified chlorinated paraffin 52 containing dihydroxy and a proper amount of p-toluenesulfonic acid are added into a reaction kettle, nitrogen is introduced into the reaction kettle, the reaction is carried out for 6 hours at 120 ℃ until no water is generated, and the reaction is stopped. Cooling, filtering and rotary steaming to obtain a crude product. Vacuum distilling to obtain Z2.
Example 3
1) Preparation of chlorinated paraffin 52 containing carboxyl group: 20g of chlorinated paraffin 52 is dissolved in 200mL of acetone, stirred and dissolved, and then 20g of p-hydroxybenzoic acid and 23g of potassium carbonate are added to react for 24h at 65 ℃ 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 chlorinated paraffin 52 containing carboxyl 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 chlorinated paraffin 52 containing acyl chloride.
3) Preparation of isocyanurate-modified chlorinated paraffin 52 monohydric alcohol: 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 201mol of chlorinated paraffin 52 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 52 containing monohydroxy isocyanurate modification.
4) Preparation of isocyanurate modified chlorinated paraffin 42 diol: 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 52 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 42 containing the binary hydroxyl isocyanurate modification.
5) Preparation of chlorinated paraffin modified by isocyanuric ester containing carboxyl: adding 100mol of carbon tetrachloride, 70mol of hydroxyl-containing isocyanurate modified chlorinated paraffin 52 and 70mol of trimellitic anhydride into a reaction kettle, introducing nitrogen into the reaction kettle, stirring and heating to 70 ℃, reacting for 3h, cooling, extracting and separating with ethyl acetate, drying an organic phase with anhydrous calcium chloride, drying for 8h, filtering under reduced pressure, and distilling the filtrate to remove the solvent to obtain the isocyanurate modified chlorinated paraffin 52 dibasic acid.
6) Preparation of polymeric flame retardant: 100mol of isocyanuric ester modified chlorinated paraffin 52 dibasic acid, 100mol of dihydric isocyanuric ester modified chlorinated paraffin 42 and a proper amount of p-toluenesulfonic acid are introduced into a reaction kettle, and the reaction is stopped after 6 hours at 130 ℃ until no water is generated. Cooling, filtering and rotary steaming to obtain a crude product. Vacuum distilling to obtain Z3.
Example 4
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 isocyanurate modified chlorinated paraffin 70 monohydric alcohol: 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 205mol 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 with anhydrous calcium chloride, drying for 8h, filtering under reduced pressure, and distilling the filtrate to remove the solvent to obtain the chlorinated paraffin 70 containing monohydroxy isocyanurate modification.
4) Preparation of isocyanurate modified chlorinated paraffin 70 dihydric alcohol: 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 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 with anhydrous calcium chloride, drying for 8h, filtering under reduced pressure, and distilling the filtrate to remove the solvent to obtain the chlorinated paraffin 70 containing the binary hydroxyl isocyanurate modification.
5) Preparation of chlorinated paraffin modified by isocyanuric ester containing carboxyl: adding 100mol of carbon tetrachloride, 70mol of hydroxyl-containing isocyanurate modified chlorinated paraffin 70 and 70mol of trimellitic anhydride into a reaction kettle, introducing nitrogen into the reaction kettle, stirring and heating to 70 ℃, reacting for 3h, cooling, extracting and separating with ethyl acetate, drying an organic phase with anhydrous calcium chloride, drying for 8h, filtering under reduced pressure, and distilling the filtrate to remove the solvent to obtain the isocyanurate modified chlorinated paraffin 70 dibasic acid.
6) Preparation of polymeric flame retardant: 100mol of isocyanuric ester modified chlorinated paraffin 70 diacid, 100mol of isocyanuric ester modified chlorinated paraffin 70 containing dihydroxy and a proper amount of p-toluenesulfonic acid are added into a reaction kettle, nitrogen is introduced into the reaction kettle, the reaction is carried out for 6 hours at 125 ℃ until no water is generated, and the reaction is stopped. Cooling, filtering and rotary steaming to obtain a crude product. Vacuum distilling to obtain Z4.
Example 5
1) Preparation of carboxyl group-containing chlorinated paraffin 70: 20g of chlorinated paraffin 70 is dissolved in 210mL of acetone, stirred and dissolved, and then 20g of p-hydroxybenzoic acid and 26g of potassium carbonate are added to react for 24h at 65 ℃ 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 50 ℃, reacting for 6 hours, cooling to room temperature, standing and layering to obtain the chlorinated paraffin 70 containing acyl chloride.
3) Preparation of isocyanurate modified chlorinated paraffin 70 monohydric alcohol: 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 202mol 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 monohydroxy isocyanurate modification.
4) Preparation of isocyanurate modified chlorinated paraffin 52 dihydric alcohol: 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 52 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 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.
5) Preparation of chlorinated paraffin modified by isocyanuric ester containing carboxyl: adding 100mol of carbon tetrachloride, 70mol of hydroxyl-containing isocyanurate modified chlorinated paraffin 70 and 70mol of trimellitic anhydride into a reaction kettle, introducing nitrogen into the reaction kettle, stirring and heating to 65 ℃, reacting for 3h, cooling, extracting and separating with ethyl acetate, drying an organic phase with anhydrous calcium chloride, drying for 8h, filtering under reduced pressure, and distilling the filtrate to remove the solvent to obtain the isocyanurate modified chlorinated paraffin 70 dibasic acid.
6) Preparation of polymeric flame retardant: 100mol of isocyanuric ester modified chlorinated paraffin 70 dibasic acid, 100mol of isocyanuric ester modified chlorinated paraffin 52 containing dihydric hydroxyl and a proper amount of p-toluenesulfonic acid are introduced into a reaction kettle, nitrogen is introduced into the reaction kettle, the reaction is carried out for 6 hours at 130 ℃ until no water is generated, and the reaction is stopped. Cooling, filtering and rotary steaming to obtain a crude product. Vacuum distilling to obtain Z5.
The inventor applies the prepared polymer flame retardant to polyvinyl chloride. Reference is made to: GB/T2406-2008 'Plastic burning Performance test method-oxygen index method' measures the flame retardant property of the product in polyvinyl chloride. Selecting different flame retardants, dioctyl phthalate (DOP) and synergistic flame retardant antimony trioxide (Sb)2O3) And polyvinyl chloride (PVC) in the proportion of the formula, extruding the mixture by using an extruder, preparing a sample strip with the length of 15cm and the diameter of 3mm, and testing the flame retardance and the physical properties of the sample strip, wherein 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 flame retardant performance data for the polymer flame retardants synthesized in inventive examples 1-5:
in conclusion, chlorinated paraffin is introduced into an isocyanurate molecular ring through a chemical bond to form dihydric alcohol and monohydric alcohol, the monohydric alcohol reacts with trimellitic anhydride to form dibasic acid, and then the dibasic acid and the trimellitic anhydride react to prepare the polymer flame retardant through a polymerization reaction.
Claims (7)
1. A polymer flame retardant characterized by comprising the following structural units:
in the above structural unit: r1、R2、R3Is a chlorinated paraffin chain segment.
2. A method of preparing a polymeric flame retardant of claim 1, comprising the steps of:
step (1): preparation of chlorinated paraffins containing carboxyl groups
Dissolving chlorinated paraffin in acetone, 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 hydroxyl-containing isocyanurate modified chlorinated Paraffin
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 or 2-2.2: 1, and respectively obtaining chlorinated paraffin containing binary or monobasic hydroxyl;
and (4): preparation of carboxyl-containing isocyanurate-modified chlorinated Paraffin
Adding the chlorinated paraffin containing the monohydric hydroxyl and trimellitic anhydride obtained in the step (3) into a reaction kettle, and reacting to obtain chlorinated paraffin containing carboxyl isocyanurate modification;
and (5): preparation of polymeric flame retardants
And (3) adding the chlorinated paraffin modified by the isocyanurates containing carboxyl obtained in the step (4), the chlorinated paraffin modified by the isocyanurates containing dihydric hydroxyl obtained in the step (3), adding a proper amount of p-toluenesulfonic acid and a proper amount of toluene or cyclohexane as a water-carrying agent into a reaction kettle, and heating to react to obtain the polymer flame retardant.
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 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 according to claim 2, wherein the chlorinated paraffin containing monohydroxy groups in the step (4) is reacted with trimellitic anhydride at a temperature of 60-80 ℃ for 3-7 h to obtain the chlorinated paraffin modified by isocyanurate containing carboxyl groups.
7. The preparation method according to claim 2, wherein the reaction conditions in the step (5) are reaction at a temperature of 120 ℃ to 190 ℃ for 5 to 10 hours.
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| CN202110059162.2A CN112877098A (en) | 2021-01-18 | 2021-01-18 | Polymer flame retardant and preparation method thereof |
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| CN202110059162.2A CN112877098A (en) | 2021-01-18 | 2021-01-18 | Polymer flame retardant and preparation method thereof |
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Application publication date: 20210601 |