CN112679538B - Synthesis method and application of dibasic acid ester oligomer flame retardant - Google Patents
Synthesis method and application of dibasic acid ester oligomer flame retardant Download PDFInfo
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Abstract
The invention relates to a synthesis method of dibasic acid ester oligomer flame retardant and application thereof in polyurethane foam, which comprises the steps of adding THPO and a catalyst with a certain mass into a container, adjusting the reaction temperature to 10-200 ℃, controlling the pressure of the whole system to be 0.5-0.8 atmospheric pressure, gradually adding dibasic acid, anhydride or acyl chloride with a certain mass, keeping the temperature for reaction for 1-5 hours after the dropwise addition is finished, and cooling to room temperature to obtain the dibasic acid ester oligomer flame retardant. The prepared flame retardant has the advantages of good compatibility with polyether/polyester polyol, high flame retardant efficiency, simple foaming process and the like, and is suitable for flame retardance of various polyurethane foams.
Description
Technical Field
The invention belongs to the technical field of preparation of dibasic acid ester oligomer flame retardants, and particularly relates to a preparation method of a dibasic acid ester oligomer flame retardant and polyurethane foam flame-retarded by using the same.
Background
Polyurethane foam (PU) is widely used for packaging building insulation materials, vehicles, furniture cushions, and electronic devices because of its characteristics of light weight, good chemical stability, excellent corrosion resistance, excellent weather resistance, and the like. Because PU has high content of carbon-hydrogen chain segments and large specific surface area, the PU is easy to decompose and burn when heated, and the Limiting Oxygen Index (LOI) of the PU is only 16-18 percent; PU produces a large amount of toxic smoke such as hydrogen cyanide, carbon monoxide and the like during combustion, and brings serious threat to the safety of life and property of people. Therefore, flame retardant modification of PU is necessary.
The trihydroxymethyl phosphine oxide (THPO) is used as a novel reaction type flame retardant, has the characteristics of high phosphorus content, good flame retardant effect, high chemical stability, no toxicity, no harm and the like, and is mainly used for flame retardance of polyurethane materials. However, during the production application, THPO is still pure in the following two disadvantages: the THPO hydroxyl value is about 1200 and is far higher than 400-500 of the polyol, so that the mechanical property of PU can be obviously reduced by adding the THPO in the foaming process; THPO is more polar and does not disperse well in polyols.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and firstly provides a dibasic acid oligomer flame retardant.
The invention also aims to provide a preparation method of the oligomer flame retardant.
It is a final object of the present invention to provide a flame retarded polyurethane foam prepared using the oligomeric flame retardant described above.
The invention provides an organic dibasic acid ester oligomer flame retardant which is characterized in that the structural general formula of the dibasic acid ester oligomer flame retardant is as follows:
Preferably, R is C 0 ～C 3 And n is a positive integer of 3 to 5.
More preferably, R is C 0 And n is 3. Or R is a linear methylene of C2, and n is 5. Or R is a linear alkylene group of 4 carbon atoms, n =8. Or R is-C = C-, n =4. Or R is phenylene and n =5.
The invention provides a preparation method of the dibasic acid ester oligomer flame retardant, which is characterized in that the method comprises the following process steps and conditions:
THPO and a certain mass of catalyst are added into a three-mouth bottle, the reaction temperature is adjusted to 10-200 ℃, the pressure of the whole system is about 0.5-0.8 atmospheric pressure, a certain mass of dibasic acid, anhydride or acyl chloride is gradually added, the temperature is kept for reaction for 1-5 hours after the dripping is finished, and the dibasic acid ester oligomer flame retardant is obtained after cooling to the room temperature.
The catalyst used in the above method is a titanium-based catalyst or a tin-based catalyst, wherein the titanium-based catalyst is tetrabutyl titanate; the tin catalyst includes stannous chloride or dibutyl tin laurate.
The dosage of the catalyst in the method is 0.05-0.25 percent of the mass of the THPO.
The dibasic acid in the above method is a fatty acid, an unsaturated acid or an aromatic acid having 2 to 8 carbon atoms; the acid anhydride or the acid chloride is formed by dibasic acid in fatty acid, unsaturated acid or aromatic acid with 2-8 carbon atoms. The dibasic acid, anhydride or acid chloride includes oxalyl chloride, 1, 4-succinic acid, terephthalic acid, or maleic anhydride.
The mole ratio of the binary acid, anhydride or acyl chloride and THPO used in the method is 0.5-1.4.
The invention also aims to use the dibasic acid ester oligomer flame retardant as a flame retardant for polyurethane.
In particular to the application of the flame retardant in polyurethane soft foam and polyurethane hard foam.
Compared with the prior art, the invention has the following beneficial effects:
1. the flame retardant provided by the invention is a reactive flame retardant, does not contain halogen, and meets the requirement of environmental protection; meanwhile, the hydroxyl value content is appropriate, and the polyurethane material can be used as a chain extender of a polyurethane material.
2. The flame retardant provided by the invention solves the problems of high hydroxyl value and poor compatibility with polyether polyol when THPO is used as a polyurethane flame retardant.
3. The polyurethane foam added with the flame retardant has the characteristics of good flame retardant effect, good foam uniformity, good dimensional stability, excellent mechanical property and the like.
4. The additive amount of the flame retardant provided by the invention is 5wt%, so that the polyurethane flexible foam can meet the requirements of Cal.T.B.117 vertical combustion test; rigid polyurethane foams can also be made to vertical burn V-0 rating.
5. The preparation method provided by the invention is simple, easy to control and convenient to popularize and use.
Drawings
FIG. 1 is a chart comparing the hydrogen nuclear magnetic resonance spectra of FR-1 and THPO flame retardants prepared in example 1.
FIG. 2 is the compatibility results of the flame retardant prepared in example 3 with polyether polyol.
FIG. 3 is a vertical burn of the flame retardant foams prepared in example 1 and comparative example 1.
Detailed Description
The invention is further illustrated by the following examples. It should be noted that the examples given are not to be construed as limiting the scope of the invention, and that those skilled in the art, on the basis of the teachings of the present invention, will be able to make numerous insubstantial modifications and adaptations of the invention without departing from its scope.
In addition, it is to be noted that the vertical burning (UL-94) of the polyurethane flexible foam prepared in the following application examples and comparative application examples was tested using a CZF-2 type vertical burner with reference to the Cal.T.B.117 standard; the vertical burning (UL-94) of rigid polyurethane foams was tested using a vertical burner of the type CZF-2 with reference to the UL-94 standard. The Limiting Oxygen Index (LOI) is tested by an HC-2C type limiting oxygen index tester according to GB/T2406.1-2008 and GB/T2406.2-2009 standards.
Example 1
Adding 1mol of THPO and dibutyltin laurate accounting for 0.05 percent of the mass of the THPO into a three-necked bottle, adjusting the temperature to 10 ℃, adjusting the pressure of the whole system to be about 0.8 atmosphere, dropwise adding 1mol of oxalyl chloride, keeping the temperature for reaction for 3 hours after dropwise adding is finished for about 1 hour, and cooling to room temperature to obtain the dibasic ester oligomer flame retardant, which is marked as FR-1.
According to the nuclear magnetic results, FR-1 has the structural formula:
the comparison graph of the nuclear magnetic resonance hydrogen spectrums of the prepared flame retardant FR-1 and THPO shows that the peak of 3.6ppm belongs to the H of the methylene of THPO, the chemical shift of the H on the methylene after the reaction with oxalyl chloride obviously moves to the high chemical shift direction and is positioned near 4.2ppm, and the successful preparation of FR-1 is proved.
Example 2
Adding 1mol of THPO and tetrabutyl titanate accounting for 0.25 percent of the mass of the THPO into a three-neck bottle, adjusting the temperature to 200 ℃, gradually adding 0.5mol of succinic acid under the pressure of about 0.8 atmosphere in the whole system, after dropwise adding for about 1 hour, keeping the temperature for reaction for 1 hour, and cooling to room temperature to obtain the dibasic acid ester oligomer flame retardant, which is marked as FR-2.
FR-2 has the structural formula:
example 3
Adding 1mol of THPO and stannous chloride accounting for 0.15 percent of the mass of the THPO into a three-mouth bottle, adjusting the temperature to 180 ℃, adjusting the pressure of the whole system to be about 0.8 atmospheric pressure, gradually adding 1.2mol of adipic acid, keeping the temperature for reaction for 5 hours after the addition of the adipic acid is finished for about 1 hour, and cooling to room temperature to obtain the dibasic acid ester oligomer flame retardant, which is marked as FR-3.
FR-3 has the structural formula:
wherein R is a linear alkylene group of 4 carbon atoms and n =8.
Example 4
Adding 1mol of THPO and stannous chloride accounting for 0.20 percent of the mass of the THPO into a three-necked bottle, adjusting the temperature to 80 ℃, dropwise adding 0.8mol of maleic anhydride under the pressure of about 0.8 atmosphere in the whole system, keeping the temperature for 2 hours after dropwise adding is finished for about 1 hour, and cooling to room temperature to obtain the dibasic acid ester oligomer flame retardant, which is marked as FR-4.
FR-4 has the structural formula:
wherein R is-C = C-, and n =4.
Example 5
Adding 1mol of THPO and tetrabutyl titanate accounting for 0.20 percent of the mass of the THPO into a three-neck bottle, adjusting the temperature to 160 ℃, gradually adding 1.4mol of terephthalic anhydride into the three-neck bottle under the pressure of about 0.8 atmosphere, keeping the temperature for reaction for 4 hours after the addition of the terephthalic anhydride is finished for about 1 hour, and cooling the mixture to room temperature to obtain the dibasic ester oligomer flame retardant, which is marked as FR-5.
FR-5 has the structural formula:
wherein R is phenylene and n =5.
Example 6
The method adopts a one-step foaming method, and comprises the following specific formula: polyether polyol: 25g of the total weight of the mixture; PEG 400:20g of the total weight of the mixture; 17g of the flame retardant prepared in example 3; water: 3g of the total weight of the mixture; chlorinated silicone oil: 2g of the total weight of the mixture; DMP-30:1g of a compound; stannous octoate: 0.3g; MDI:105g (comparative example 1 without the flame retardant prepared in example 3); firstly, white materials are evenly mixed by mechanical stirring in a plastic beaker, then black materials, namely isocyanate, are quickly poured into the materials and stirred for 10s at the speed of 2000r/min, then the materials are quickly poured into a mould at the temperature of 80 ℃, and the materials are respectively cured for 2h at the temperature of 80 ℃ and 120 ℃ to be cured. The foam had a limiting oxygen index of 24% and extinguished on vertical burning. The foam of comparative example 1 without the flame retardant prepared in example 3 had a limiting oxygen index of 20% and was electrodeless with vertical burning.
FIG. 2 illustrates that the flame retardant prepared in example 3 is well soluble in polyether polyol, while THPO is poorly soluble in polyether polyol, and the improved solubility facilitates its use in polyurethane. The dissolution effect of the flame retardants of examples 1, 2, 4, 5 was the same as that of example 3, and for this reason, the drawings are not repeated. Meanwhile, the flame retardant synthesized in the embodiments 1 to 5 also has similar compatibility with polyether polyol in polyester polyol.
Example 7
12 parts of the prepared flame retardant of example 1 were mixed with 100 parts of polyether polyol, 3 parts of water, 0.4 part of triethylenediamine, 0.5 part of dibutyltin dilaurate and 1 part of silicone oil for soft foams under high-speed stirring, stirred with toluene diisocyanate under high-speed stirring for 6 seconds, immediately poured into a mold, and cured at room temperature for 72 hours (the prepared flame retardant of example 3 was not added as comparative example 2). The foam had a limiting oxygen index of 24.5% and the vertical burn extinguished. Whereas the foam of comparative example 2 had a limiting oxygen index of 18% and was fired vertically to the jig.
FIG. 3 shows the vertical burning of the flame retardant foams prepared in application example 1 and application comparative example 1, wherein the flame retardant foams added with the flame retardant have obvious flame retardant performance and can be instantly ignited after leaving fire to reach the vertical burning V-0 level.
Example 8
The same foaming process as in example 6 and example 7 was used to apply the flame retardants FR-1, FR-2, FR-3, FR-4, FR-5 prepared in examples 1 to 5 to the flexible polyurethane foam and the rigid polyurethane foam, respectively, with the addition of 5wt% of the flame retardant in the rigid foam and 10.2% of the flame retardant in the flexible foam (based on 100 parts of the polyether polyol as described in example 7). The concrete effects are as follows:
| case(s) | Limiting oxygen index of flame-retardant polyurethane rigid foam | Limiting oxygen index of flame-retardant polyurethane flexible foam |
| FR-1 | 25.0％ | 24.5％ |
| FR-2 | 24.3％ | 24.0％ |
| FR-3 | 24.0％ | 23.5％ |
| FR-4 | 25.2％ | 24.0％ |
| FR-5 | 24.5％ | 24.2％ |
| Comparative example 1 | 20％ | 18％ |
Claims (8)
1. The dibasic acid ester oligomer flame retardant is characterized by having the following structural general formula:
2. The dibasic acid ester oligomer flame retardant of claim 1, wherein R is C 0 ～C 3 Straight or branched alkylene, alkenylene, or alkenylene ofPhenyl and n is a positive integer of 3 to 5.
3. The dibasic acid ester oligomer flame retardant of claim 1, wherein R is C 0 And n is 3.
4. The method for synthesizing the dibasic acid ester oligomer flame retardant according to any one of claims 1 to 3, which is characterized by comprising the following steps of:
adding THPO and a certain mass of catalyst into a container, adjusting the reaction temperature to 10-200 ℃, adjusting the pressure of the whole system to 0.5-0.8 atmospheric pressure, gradually adding a certain mass of dibasic acid, anhydride or acyl chloride, keeping the temperature for reaction for 1-5 hours after the dropwise addition is finished, and cooling to room temperature to obtain the dibasic acid ester oligomer flame retardant, wherein the catalyst is a titanium catalyst or a tin catalyst, and the titanium catalyst is tetrabutyl titanate; the tin catalyst is stannous chloride or dibutyl tin laurate, and the dibasic acid is fatty acid or aromatic acid with 2-8 carbon atoms; the acid anhydride or the acid chloride is formed by dibasic acid in fatty acid or aromatic acid with 2-8 carbon atoms.
5. The method for synthesizing dibasic acid ester oligomer flame retardant according to claim 4, wherein the amount of the catalyst is 0.05-0.25% of the mass of THPO.
6. The method for synthesizing dibasic acid ester oligomer flame retardant according to claim 4, wherein the dibasic acid, anhydride or acid chloride is oxalyl chloride, 1, 4-succinic acid, terephthalic acid or maleic anhydride.
7. The method for synthesizing dibasic acid ester oligomer flame retardant according to claim 4, wherein the molar ratio of dibasic acid, anhydride or acyl chloride to THPO is 0.5-1.4.
8. Use of the dibasic acid ester oligomer flame retardant according to any one of claims 1 to 3 as a flame retardant for polyurethane.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6440521A (en) * | 1987-08-05 | 1989-02-10 | Toray Industries | Production of polyester |
| JP2003040957A (en) * | 2001-08-01 | 2003-02-13 | Nippon Chem Ind Co Ltd | Phosphorus-containing resol-type phenol resin, its production method, phenol resin composition and laminated board |
| CN103980313A (en) * | 2014-05-23 | 2014-08-13 | 厦门大学 | Phosphorus-nitrogen synergistic flame-retardant polyalcohol and preparation method thereof |
| CN110078909A (en) * | 2019-04-28 | 2019-08-02 | 上海元业体育科技有限公司 | A kind of phosphorous silane-terminated polyether and preparation method thereof |
| CN111995747A (en) * | 2020-09-15 | 2020-11-27 | 湖北省兴发磷化工研究院有限公司 | Preparation method and application of reactive flame retardant for polyamide |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6440521A (en) * | 1987-08-05 | 1989-02-10 | Toray Industries | Production of polyester |
| JP2003040957A (en) * | 2001-08-01 | 2003-02-13 | Nippon Chem Ind Co Ltd | Phosphorus-containing resol-type phenol resin, its production method, phenol resin composition and laminated board |
| CN103980313A (en) * | 2014-05-23 | 2014-08-13 | 厦门大学 | Phosphorus-nitrogen synergistic flame-retardant polyalcohol and preparation method thereof |
| CN110078909A (en) * | 2019-04-28 | 2019-08-02 | 上海元业体育科技有限公司 | A kind of phosphorous silane-terminated polyether and preparation method thereof |
| CN111995747A (en) * | 2020-09-15 | 2020-11-27 | 湖北省兴发磷化工研究院有限公司 | Preparation method and application of reactive flame retardant for polyamide |
Non-Patent Citations (1)
| Title |
|---|
| "一种新型磷酸酯类阻燃剂的合成方法研究";田路等;《科教导刊(电子版)》;20181231(第12期);第288+296页 * |
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